JP7455973B2 - Thermoplastic resin composition, method for producing the same, and molded articles produced therefrom - Google Patents
Thermoplastic resin composition, method for producing the same, and molded articles produced therefrom Download PDFInfo
- Publication number
- JP7455973B2 JP7455973B2 JP2022529071A JP2022529071A JP7455973B2 JP 7455973 B2 JP7455973 B2 JP 7455973B2 JP 2022529071 A JP2022529071 A JP 2022529071A JP 2022529071 A JP2022529071 A JP 2022529071A JP 7455973 B2 JP7455973 B2 JP 7455973B2
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- JP
- Japan
- Prior art keywords
- weight
- resin composition
- thermoplastic resin
- compound
- methylstyrene
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 75
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- -1 aromatic vinyl compound Chemical class 0.000 claims description 113
- 229920005989 resin Polymers 0.000 claims description 50
- 239000011347 resin Substances 0.000 claims description 50
- 229920000578 graft copolymer Polymers 0.000 claims description 44
- 229920002554 vinyl polymer Polymers 0.000 claims description 39
- 229920001971 elastomer Polymers 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 31
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 30
- 229920000193 polymethacrylate Polymers 0.000 claims description 29
- 229920001577 copolymer Polymers 0.000 claims description 27
- 238000012360 testing method Methods 0.000 claims description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 239000000314 lubricant Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 14
- DEAKWVKQKRNPHF-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 DEAKWVKQKRNPHF-UHFFFAOYSA-N 0.000 claims description 14
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000012760 heat stabilizer Substances 0.000 claims description 9
- 239000012963 UV stabilizer Substances 0.000 claims description 7
- 239000012748 slip agent Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000088 plastic resin Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 description 48
- 239000007924 injection Substances 0.000 description 48
- 239000000047 product Substances 0.000 description 28
- 230000000694 effects Effects 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 18
- 230000000704 physical effect Effects 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 14
- 239000000049 pigment Substances 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 10
- 239000008188 pellet Substances 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- 238000012662 bulk polymerization Methods 0.000 description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000001841 imino group Chemical group [H]N=* 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229940037312 stearamide Drugs 0.000 description 5
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- 239000003017 thermal stabilizer Substances 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 229920006015 heat resistant resin Polymers 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920000638 styrene acrylonitrile Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UKJARPDLRWBRAX-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine Chemical compound C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 UKJARPDLRWBRAX-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- ABFCPWCUXLLRSC-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C ABFCPWCUXLLRSC-UHFFFAOYSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 1
- KQJQPCJDKBKSLV-UHFFFAOYSA-N 1-bromo-3-ethenylbenzene Chemical compound BrC1=CC=CC(C=C)=C1 KQJQPCJDKBKSLV-UHFFFAOYSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- BWJKLDGAAPQXGO-UHFFFAOYSA-N 2,2,6,6-tetramethyl-4-octadecoxypiperidine Chemical compound CCCCCCCCCCCCCCCCCCOC1CC(C)(C)NC(C)(C)C1 BWJKLDGAAPQXGO-UHFFFAOYSA-N 0.000 description 1
- HPFMMFGKGWOEPG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound OC1=C(C=C(C=C1)C(C)(C)CC(C)(C)C)N1N=C2C(=N1)C=CC=C2.OC2=C(C=C(C=C2)C(CC(C)(C)C)(C)C)N2N=C1C(=N2)C=CC=C1 HPFMMFGKGWOEPG-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- CHNGPLVDGWOPMD-UHFFFAOYSA-N 2-ethylbutyl 2-methylprop-2-enoate Chemical compound CCC(CC)COC(=O)C(C)=C CHNGPLVDGWOPMD-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- GUCMKIKYKIHUTM-UHFFFAOYSA-N 3,3,5,5-tetramethyl-1-[2-(3,3,5,5-tetramethyl-2-oxopiperazin-1-yl)ethyl]piperazin-2-one Chemical compound O=C1C(C)(C)NC(C)(C)CN1CCN1C(=O)C(C)(C)NC(C)(C)C1 GUCMKIKYKIHUTM-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- BYMLDFIJRMZVOC-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O BYMLDFIJRMZVOC-UHFFFAOYSA-N 0.000 description 1
- CCMZKOAOMQSOQA-UHFFFAOYSA-N 3-methyl-2-methylidenebutanenitrile Chemical compound CC(C)C(=C)C#N CCMZKOAOMQSOQA-UHFFFAOYSA-N 0.000 description 1
- HPFWYRKGZUGGPB-UHFFFAOYSA-N 4,6-dichloro-n-(2,4,4-trimethylpentan-2-yl)-1,3,5-triazin-2-amine Chemical compound CC(C)(C)CC(C)(C)NC1=NC(Cl)=NC(Cl)=N1 HPFWYRKGZUGGPB-UHFFFAOYSA-N 0.000 description 1
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- GQEFPXSNRRKUHO-UHFFFAOYSA-N 4-methylpent-1-enylbenzene Chemical compound CC(C)CC=CC1=CC=CC=C1 GQEFPXSNRRKUHO-UHFFFAOYSA-N 0.000 description 1
- XTJYYRKHFBFRJV-UHFFFAOYSA-N CC1(NC(CC(C1)C(C(=O)O)N(C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)(C)C)C Chemical compound CC1(NC(CC(C1)C(C(=O)O)N(C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)(C)C)C XTJYYRKHFBFRJV-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- OSIVCXJNIBEGCL-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCCCCCCCC)C(C)(C)C1 OSIVCXJNIBEGCL-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- SKGVGRLWZVRZDC-UHFFFAOYSA-N butyl 2-sulfanylacetate Chemical compound CCCCOC(=O)CS SKGVGRLWZVRZDC-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- RRZCFXQTVDJDGF-UHFFFAOYSA-N dodecyl 3-(3-octadecoxy-3-oxopropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC RRZCFXQTVDJDGF-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- MYWWWNVEZBAKHR-UHFFFAOYSA-N methyl 3-(3-methoxy-3-oxopropyl)sulfanylpropanoate Chemical compound COC(=O)CCSCCC(=O)OC MYWWWNVEZBAKHR-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- JQTFPHLEQLLQOT-UHFFFAOYSA-N octadecyl 2-sulfanylacetate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CS JQTFPHLEQLLQOT-UHFFFAOYSA-N 0.000 description 1
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 1
- MADOXCFISYCULS-UHFFFAOYSA-N octyl 2-sulfanylacetate Chemical compound CCCCCCCCOC(=O)CS MADOXCFISYCULS-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- ZPNJBTBYIHBSIG-UHFFFAOYSA-N phenyl-(2,2,6,6-tetramethylpiperidin-4-yl)methanone Chemical compound C1C(C)(C)NC(C)(C)CC1C(=O)C1=CC=CC=C1 ZPNJBTBYIHBSIG-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Description
〔関連出願との相互参照〕
本出願は、２０２０年０９月１５日付の韓国特許出願第１０－２０２０－０１１８５２８号及びこれに基づいて２０２１年０７月１５日付で再出願された韓国特許出願第１０－２０２１－００９３００４号に基づく優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として組み込まれる。
[Cross reference with related applications]
This application has priority based on Korean Patent Application No. 10-2020-0118528 dated September 15, 2020 and Korean Patent Application No. 10-2021-0093004, which was refiled on July 15, 2021 based on this. All contents claimed and disclosed in the documents of the Korean patent application are incorporated as part of this specification.
本発明は、熱可塑性樹脂組成物、その製造方法及びそれから製造された成形品に関し、より詳細には、耐衝撃性、耐熱度及び流動性に優れ、特に、面衝撃強度（Ｍｕｌｔｉ－ａｘｉａｌ ｉｍｐａｃｔ ｓｔｒｅｎｇｔｈ）が高いながらも、その標準偏差が低いため大型製品を射出成形することができ、ディープブラック（ｄｅｅｐ ｂｌａｃｋ）色相の実現が可能であると共に、ゴニオクロミズム（Ｇｏｎｉｏｃｈｒｏｍｉｓｍ）現象の発生を抑制して射出外観品質及び自動車の信頼性評価を満たす熱可塑性樹脂組成物、その製造方法及びそれから製造された成形品に関する。 The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article produced from the same. ), but its standard deviation is low, making it possible to injection mold large products, achieving a deep black hue, and suppressing the occurrence of goniochromism during injection molding. The present invention relates to a thermoplastic resin composition that satisfies appearance quality and automobile reliability evaluation, a method for producing the same, and a molded article produced from the same.
自動車外装材を無塗装で使用するためには、優れた射出外観品質と共に、自動車の信頼性評価を満たし得る物性が求められる。特にラジエーターグリルに適用するためには、大型射出製品の成形が可能なように樹脂の流れ性、高いレベルの耐熱度及び衝撃強度が必要であり、主要な信頼性評価と関連する面衝撃強度特性が求められる。このために、ディープブラック色相の実現のためのＭＭＡ系樹脂と、耐熱度の実現のための耐熱性樹脂とを混合しなければならないが、２つの樹脂の相溶性が良くないため、所望のレベルの射出外観品質及び均一な物性の実現が難しい。相溶性が良くない２つの樹脂を混用する場合、ゴニオクロミズム現象が発生し、物性のばらつきが大きくなる。特に自動車の主要な信頼性評価の項目である面衝撃強度の標準偏差値が高くなるという問題がある。 In order to use unpainted automotive exterior materials, excellent injection appearance quality and physical properties that can satisfy automotive reliability evaluations are required. Particularly for applications in radiator grilles, resin flowability, high levels of heat resistance and impact strength are required to enable molding of large injection products, and surface impact strength properties associated with key reliability evaluations are required. is required. For this purpose, it is necessary to mix an MMA-based resin to achieve a deep black hue and a heat-resistant resin to achieve heat resistance, but since the two resins are not compatible, it is difficult to achieve the desired level. It is difficult to achieve injection appearance quality and uniform physical properties. When two resins with poor compatibility are used together, a goniochromism phenomenon occurs, resulting in large variations in physical properties. In particular, there is a problem in that the standard deviation value of surface impact strength, which is a major reliability evaluation item for automobiles, becomes high.
したがって、耐熱度及び耐衝撃性を有すると共に、高黒色の実現及び大型射出製品の成形が可能であり、射出外観品質を改善させることができる熱可塑性樹脂組成物の開発が求められている。 Therefore, there is a need for the development of a thermoplastic resin composition that has heat resistance and impact resistance, can realize high black color, can be molded into large-sized injection products, and can improve the quality of injection appearance.
上記の従来技術の問題点を解決するために、本発明は、耐衝撃性、耐熱度及び流動性に優れ、特に平均面衝撃強度が高いながらも、その標準偏差が低いため大型製品を射出成形することができ、ディープブラック色相の実現が可能であると共に、ゴニオクロミズム（Ｇｏｎｉｏｃｈｒｏｍｉｓｍ）現象の発生を抑制して射出外観品質及び自動車の信頼性評価を満たす熱可塑性樹脂組成物、その製造方法及びそれから製造された成形品を提供することを目的とする。 In order to solve the above-mentioned problems of the prior art, the present invention has excellent impact resistance, heat resistance, and fluidity, and in particular, has a high average surface impact strength and a low standard deviation, so large products can be injection molded. A thermoplastic resin composition capable of realizing a deep black hue, suppressing the occurrence of a goniochromism phenomenon, and satisfying injection appearance quality and reliability evaluation of an automobile, a method for producing the same, and the like. The purpose is to provide manufactured molded products.
本発明の上記目的及びその他の目的は、以下で説明する本発明によって全て達成することができる。 The above objects and other objects of the present invention can all be achieved by the present invention described below.
上記の目的を達成するために、本発明は、Ａ－１）平均粒径２００～４００ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体３～２２重量％と；Ａ－２）平均粒径５０～１９９ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体１７～４０重量％と；Ｂ）（メタ）アクリル酸アルキルエステル化合物、α－メチルスチレン系化合物及びビニルシアン化合物を含んでなる共重合体３０～５７重量％と；Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）６～３０重量％と；を含み、ＩＳＯ ６６０３－２に準拠して、速度４．４ｍ／ｓ下で試験片の厚さ２．０ｍｍで最大荷重エネルギーを１０回測定した平均面衝撃強度が２２Ｊ以上であり、標準偏差が６．５以下であることを特徴とする熱可塑性樹脂組成物を提供する。 In order to achieve the above object, the present invention provides A-1) 3 to 22% by weight of a graft copolymer comprising an acrylate rubber having an average particle size of 200 to 400 nm, an aromatic vinyl compound, and a vinyl cyanide compound. and; A-2) 17 to 40% by weight of a graft copolymer comprising an acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound having an average particle size of 50 to 199 nm; and B) (meth)acrylic acid alkyl ester. C) 6 to 30% by weight of a polymethacrylate resin (excluding α-methylstyrene); , in accordance with ISO 6603-2, the average surface impact strength measured 10 times at the maximum load energy with a test piece thickness of 2.0 mm at a speed of 4.4 m/s is 22 J or more, and the standard deviation is 6. 5 or less.
また、本発明は、Ａ－１）平均粒径２００～４００ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体３～２２重量％と；Ａ－２）平均粒径５０～１９９ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体１７～４０重量％と；Ｂ）（メタ）アクリル酸アルキルエステル化合物、α－メチルスチレン系化合物及びビニルシアン化合物を含んでなる共重合体３０～５７重量％と；Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）６～３０重量％と；を含み、ＩＳＯ ６６０３－２に準拠して、速度４．４ｍ／ｓ下で試験片の厚さ２．０ｍｍで最大荷重エネルギーを１０回測定した平均面衝撃強度が２２Ｊ以上であり、標準偏差が６．５以下であり、前記Ｂ）共重合体は、（メタ）アクリル酸アルキルエステル化合物３０～５５重量％、α－メチルスチレン系化合物２５～５０重量％及びビニルシアン化合物１０～３０重量％を含んでなることを特徴とする熱可塑性樹脂組成物を提供することができる。 Further, the present invention provides A-1) 3 to 22% by weight of a graft copolymer comprising an acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound having an average particle size of 200 to 400 nm; 17 to 40% by weight of a graft copolymer comprising an acrylate rubber having a particle size of 50 to 199 nm, an aromatic vinyl compound, and a vinyl cyanide compound; B) a (meth)acrylic acid alkyl ester compound, an α-methylstyrene compound; C) 6-30% by weight of a polymethacrylate resin (excluding α-methylstyrene), and complies with ISO 6603-2. The average surface impact strength obtained by measuring the maximum load energy 10 times at a speed of 4.4 m/s with a test piece thickness of 2.0 mm is 22 J or more, the standard deviation is 6.5 or less, and the above B ) The copolymer contains 30 to 55% by weight of a (meth)acrylic acid alkyl ester compound, 25 to 50% by weight of an α-methylstyrene compound, and 10 to 30% by weight of a vinyl cyanide compound. A plastic resin composition can be provided.
また、本発明は、Ａ－１）平均粒径２００～４００ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体３～２２重量％と；Ａ－２）平均粒径５０～１９９ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体１７～４０重量％と；Ｂ）（メタ）アクリル酸アルキルエステル化合物、α－メチルスチレン系化合物及びビニルシアン化合物を含んでなる共重合体３０～５７重量％と；Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）６～３０重量％と；を含み、ＩＳＯ ６６０３－２に準拠して、速度４．４ｍ／ｓ下で試験片の厚さ２．０ｍｍで最大荷重エネルギーを１０回測定した平均面衝撃強度が２２Ｊ以上であり、標準偏差が６．５以下であり、前記Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）は、メタクリレート単量体を５５重量％以上含んでなることを特徴とする熱可塑性樹脂組成物を提供することができる。 Further, the present invention provides A-1) 3 to 22% by weight of a graft copolymer comprising an acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound having an average particle size of 200 to 400 nm; 17 to 40% by weight of a graft copolymer comprising an acrylate rubber having a particle size of 50 to 199 nm, an aromatic vinyl compound, and a vinyl cyanide compound; B) a (meth)acrylic acid alkyl ester compound, an α-methylstyrene compound; C) 6-30% by weight of a polymethacrylate resin (excluding α-methylstyrene), and complies with ISO 6603-2. The average surface impact strength obtained by measuring the maximum load energy 10 times with a test piece thickness of 2.0 mm at a speed of 4.4 m/s is 22 J or more, the standard deviation is 6.5 or less, and the above C ) The polymethacrylate resin (excluding α-methylstyrene) can provide a thermoplastic resin composition characterized in that it contains 55% by weight or more of a methacrylate monomer.
また、本発明は、Ａ－１）平均粒径２００～４００ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体３～２２重量％と、Ａ－２）平均粒径５０～１９９ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体１７～４０重量％と、Ｂ）（メタ）アクリル酸アルキルエステル化合物、α－メチルスチレン系化合物及びビニルシアン化合物を含んでなる共重合体３０～５７重量％と、Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）６～３０重量％とを混合した後、２００～３００℃下で１０～１００ファイ規格で押出混練機を用いて熱可塑性樹脂組成物を製造するステップを含み、製造された熱可塑性樹脂組成物は、ＩＳＯ ６６０３－２に準拠して、速度４．４ｍ／ｓ下で試験片の厚さ２．０ｍｍで最大荷重エネルギーを１０回測定した平均面衝撃強度が２２Ｊ以上であり、標準偏差が６．５以下であることを特徴とする熱可塑性樹脂組成物の製造方法を提供する。 Further, the present invention provides A-1) 3 to 22% by weight of a graft copolymer comprising an acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound having an average particle size of 200 to 400 nm; 17 to 40% by weight of a graft copolymer comprising an acrylate rubber having a particle size of 50 to 199 nm, an aromatic vinyl compound, and a vinyl cyan compound, and B) a (meth)acrylic acid alkyl ester compound, an α-methylstyrene compound. After mixing 30 to 57% by weight of a copolymer containing a compound and a vinyl cyanide compound and 6 to 30% by weight of C) polymethacrylate resin (excluding α-methylstyrene), the mixture was heated at 200 to 300°C. manufacturing a thermoplastic resin composition using an extrusion kneader with a standard of 10 to 100 phi at a speed of 4.4 m/s in accordance with ISO 6603-2. Production of a thermoplastic resin composition characterized by having an average surface impact strength of 22 J or more and a standard deviation of 6.5 or less when the maximum load energy is measured 10 times with a test piece having a thickness of 2.0 mm as described below. provide a method.
また、本発明は、Ａ－１）平均粒径２００～４００ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体３～２２重量％と、Ａ－２）平均粒径５０～１９９ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体１７～４０重量％と、Ｂ）（メタ）アクリル酸アルキルエステル化合物、α－メチルスチレン系化合物及びビニルシアン化合物を含んでなる共重合体３０～５７重量％と、Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）６～３０重量％とを混合した後、２００～３００℃下で１０～１００ファイ規格で押出混練機を用いて熱可塑性樹脂組成物を製造するステップを含み、製造された熱可塑性樹脂組成物は、ＩＳＯ ６６０３－２に準拠して、速度４．４ｍ／ｓ下で試験片の厚さ２．０ｍｍで最大荷重エネルギーを１０回測定した平均面衝撃強度が２２Ｊ以上であり、標準偏差が６．５以下であり、前記Ｂ）共重合体は、（メタ）アクリル酸アルキルエステル化合物３０～５５重量％、α－メチルスチレン系化合物２５～５０重量％及びビニルシアン化合物１０～３０重量％を含んでなることを特徴とする熱可塑性樹脂組成物の製造方法を提供することができる。 Further, the present invention provides A-1) 3 to 22% by weight of a graft copolymer comprising an acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound having an average particle size of 200 to 400 nm; 17 to 40% by weight of a graft copolymer comprising an acrylate rubber having a particle size of 50 to 199 nm, an aromatic vinyl compound, and a vinyl cyan compound, and B) a (meth)acrylic acid alkyl ester compound, an α-methylstyrene compound. After mixing 30 to 57% by weight of a copolymer containing a compound and a vinyl cyanide compound and 6 to 30% by weight of C) polymethacrylate resin (excluding α-methylstyrene), the mixture was heated at 200 to 300°C. manufacturing a thermoplastic resin composition using an extrusion kneader with a standard of 10 to 100 phi at a speed of 4.4 m/s in accordance with ISO 6603-2. The average surface impact strength obtained by measuring the maximum load energy 10 times with a test piece having a thickness of 2.0 mm below is 22 J or more, and the standard deviation is 6.5 or less, and the above B) copolymer is (meta) Provided is a method for producing a thermoplastic resin composition comprising 30 to 55% by weight of an acrylic acid alkyl ester compound, 25 to 50% by weight of an α-methylstyrene compound, and 10 to 30% by weight of a vinyl cyanide compound. can do.
また、本発明は、Ａ－１）平均粒径２００～４００ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体３～２２重量％と、Ａ－２）平均粒径５０～１９９ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体１７～４０重量％と、Ｂ）（メタ）アクリル酸アルキルエステル化合物、α－メチルスチレン系化合物及びビニルシアン化合物を含んでなる共重合体３０～５７重量％と、Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）６～３０重量％とを混合した後、２００～３００℃下で１０～１００ファイ規格で押出混練機を用いて熱可塑性樹脂組成物を製造するステップを含み、製造された熱可塑性樹脂組成物は、ＩＳＯ ６６０３－２に準拠して、速度４．４ｍ／ｓ下で試験片の厚さ２．０ｍｍで最大荷重エネルギーを１０回測定した平均面衝撃強度が２２Ｊ以上であり、標準偏差が６．５以下であり、前記Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）は、メタクリレート単量体を５５重量％以上含んでなることを特徴とする熱可塑性樹脂組成物の製造方法を提供することができる。 Further, the present invention provides A-1) 3 to 22% by weight of a graft copolymer comprising an acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound having an average particle size of 200 to 400 nm; 17 to 40% by weight of a graft copolymer comprising an acrylate rubber having a particle size of 50 to 199 nm, an aromatic vinyl compound, and a vinyl cyan compound, and B) a (meth)acrylic acid alkyl ester compound, an α-methylstyrene compound. After mixing 30 to 57% by weight of a copolymer containing a compound and a vinyl cyanide compound and 6 to 30% by weight of C) polymethacrylate resin (excluding α-methylstyrene), the mixture was heated at 200 to 300°C. manufacturing a thermoplastic resin composition using an extrusion kneader with a standard of 10 to 100 phi at a speed of 4.4 m/s in accordance with ISO 6603-2. The average surface impact strength obtained by measuring the maximum load energy 10 times with a test piece thickness of 2.0 mm below is 22 J or more, the standard deviation is 6.5 or less, and the above C) polymethacrylate resin (however, α- (excluding methylstyrene) can provide a method for producing a thermoplastic resin composition characterized in that it contains 55% by weight or more of a methacrylate monomer.
また、本発明は、前記熱可塑性樹脂組成物を含むことを特徴とする成形品を提供する。 Further, the present invention provides a molded article containing the thermoplastic resin composition.
本発明によれば、耐衝撃性、耐熱度及び流動性に優れ、特に平均面衝撃強度が高いながらも、その標準偏差が低いため大型製品を射出成形することができ、ディープブラック色相の実現が可能であると共に、ゴニオクロミズム（Ｇｏｎｉｏｃｈｒｏｍｉｓｍ）現象の発生を抑制して射出外観品質及び自動車の信頼性評価を満たす熱可塑性樹脂組成物、その製造方法及びそれから製造された成形品を提供する効果がある。 According to the present invention, it has excellent impact resistance, heat resistance, and flowability, and in particular, has a high average surface impact strength, but its standard deviation is low, so large products can be injection molded, and deep black hue can be realized. In addition, it is effective to provide a thermoplastic resin composition, a method for producing the same, and a molded article produced therefrom by suppressing the occurrence of the goniochromism phenomenon and satisfying injection appearance quality and automobile reliability evaluation. .
以下、本記載の熱可塑性樹脂組成物、その製造方法及びそれから製造された成形品を詳細に説明する。 Hereinafter, the thermoplastic resin composition, the method for producing the same, and the molded article produced therefrom will be explained in detail.
本発明者らは、耐熱樹脂とＭＭＡ系樹脂との相溶性を改善するために、平均粒径が異なる２種のＡＳＡ樹脂を所定の含量に調整し、（メタ）アクリル酸アルキルエステル化合物、α－メチルスチレン系化合物及びビニルシアン化合物を含んでなる共重合体及びポリメタクリレート樹脂（但し、α－メチルスチレンを除く）を所定の含量に調整する場合、ゴニオクロミズム現象が発生せず、ディープブラック色相を実現することができ、面衝撃強度が向上し、その標準偏差が減少する効果を確認し、これに基づいてさらに研究に邁進して本発明を完成するようになった。 In order to improve the compatibility between the heat-resistant resin and the MMA-based resin, the present inventors adjusted two types of ASA resins with different average particle sizes to a predetermined content, and added a (meth)acrylic acid alkyl ester compound, α - When adjusting the content of a copolymer containing a methylstyrene compound and a vinyl cyanide compound and a polymethacrylate resin (excluding α-methylstyrene) to a predetermined content, goniochromism does not occur and a deep black hue is obtained. It was confirmed that the surface impact strength was improved and the standard deviation thereof was reduced.Based on this, the present invention was completed by further research.
本発明の熱可塑性樹脂組成物は、Ａ－１）平均粒径２００～４００ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体３～２２重量％と；Ａ－２）平均粒径５０～１９９ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体１７～４０重量％と；Ｂ）（メタ）アクリル酸アルキルエステル化合物、α－メチルスチレン系化合物及びビニルシアン化合物を含んでなる共重合体３０～５７重量％と；Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）６～３０重量％と；を含み、ＩＳＯ ６６０３－２に準拠して、速度４．４ｍ／ｓ下で試験片の厚さ２．０ｍｍで最大荷重エネルギーを１０回測定した平均面衝撃強度が２２Ｊ／ｍｍ以上であり、標準偏差が６．５以下であることを特徴とする。このような場合、耐衝撃性、耐熱度及び流動性に優れるため大型製品を射出成形することができるだけでなく、ディープブラック色相の実現が可能であり、ゴニオクロミズム（Ｇｏｎｉｏｃｈｒｏｍｉｓｍ）現象の発生を抑制して射出外観品質及び自動車の信頼性評価を満たすという効果がある。 The thermoplastic resin composition of the present invention comprises A-1) 3 to 22% by weight of a graft copolymer comprising an acrylate rubber having an average particle size of 200 to 400 nm, an aromatic vinyl compound, and a vinyl cyanide compound; -2) 17 to 40% by weight of a graft copolymer comprising an acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide compound having an average particle size of 50 to 199 nm; B) a (meth)acrylic acid alkyl ester compound, α - 30 to 57% by weight of a copolymer comprising a methylstyrene compound and a vinyl cyanide compound; and C) 6 to 30% by weight of a polymethacrylate resin (excluding α-methylstyrene); ISO 6603 -2, the average surface impact strength obtained by measuring the maximum load energy 10 times with a test piece thickness of 2.0 mm at a speed of 4.4 m/s is 22 J/mm or more, and the standard deviation is 6.5. It is characterized by the following: In such cases, it not only allows injection molding of large products due to its excellent impact resistance, heat resistance, and flowability, but also enables the realization of a deep black hue, suppressing the occurrence of the goniochromism phenomenon. This has the effect of satisfying injection appearance quality and automobile reliability evaluation.
以下、本発明の熱可塑性樹脂組成物を構成別に詳細に説明する。 Hereinafter, the thermoplastic resin composition of the present invention will be explained in detail according to its composition.
Ａ－１）平均粒径２００～４００ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体
前記グラフト共重合体のアクリレートゴムは、一例として、平均粒径が２００～４００ｎｍ、好ましくは２２０～３５０ｎｍ、より好ましくは２５０～３３０ｎｍであるが、この範囲内で、最終製造される熱可塑性樹脂組成物に、優れた耐候性、着色性、光沢性、衝撃強度及び表面特性を付与することができる。
A-1) A graft copolymer comprising an acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide compound having an average particle size of 200 to 400 nm The acrylate rubber of the graft copolymer has an average particle size of 200 to 400 nm, for example. -400nm, preferably 220-350nm, more preferably 250-330nm, but within this range, the final produced thermoplastic resin composition has excellent weather resistance, colorability, gloss, impact strength and surface. Characteristics can be given.
本記載において、平均粒径は、動的光散乱法（Ｄｙｎａｍｉｃ ｌｉｇｈｔ ｓｃａｔｔｅｒｉｎｇ）を用いて測定することができ、詳細には、粒子測定器（製品名：Ｎｉｃｏｍｐ３８０、製造社：ＰＳＳ）を用いてガウス（Ｇａｕｓｓｉａｎ）モードでインテンシティ（ｉｎｔｅｎｓｉｔｙ）値で測定する。このとき、具体的な測定例として、サンプルは、ラテックス（ＴＳＣ３５～５０ｗｔ％）０．１ｇを脱イオン水又は蒸留水で１，０００～５，０００倍希釈し、すなわち、強度セットポイント（Ｉｎｔｅｎｓｉｔｙ Ｓｅｔｐｏｉｎｔ） ３００ｋＨｚを大きく外れないように適切に希釈し、ガラス管（ｇｌａｓｓ ｔｕｂｅ）に入れて準備し、測定方法は、自動希釈（Ａｕｔｏ－ｄｉｌｕｔｉｏｎ）してフローセル（ｆｌｏｗ ｃｅｌｌ）で測定し、測定モードは、動的光散乱法（ｄｙｎａｍｉｃ ｌｉｇｈｔ ｓｃａｔｔｅｒｉｎｇ）／強度（Ｉｎｔｅｎｓｉｔｙ） ３００ＫＨｚ／強度－荷重ガウス分析（Ｉｎｔｅｎｓｉｔｙ－ｗｅｉｇｈｔ Ｇａｕｓｓｉａｎ Ａｎａｌｙｓｉｓ）とし、設定（ｓｅｔｔｉｎｇ）値は、温度２３℃、測定波長６３２．８ｎｍ、チャンネル幅（ｃｈａｎｎｅｌ ｗｉｄｔｈ） １０μｓｅｃとして測定することができる。 In this description, the average particle size can be measured using dynamic light scattering, and in detail, the average particle size can be measured using a Gaussian particle size measuring device (product name: Nicomp380, manufacturer: PSS). The intensity value is measured in (Gaussian) mode. At this time, as a specific measurement example, the sample was prepared by diluting 0.1 g of latex (TSC 35 to 50 wt%) 1,000 to 5,000 times with deionized water or distilled water, that is, the intensity set point. ) Appropriately diluted so as not to deviate significantly from 300kHz, put it in a glass tube, and prepared it.The measurement method was to auto-dilute it and measure it with a flow cell, and the measurement mode was , dynamic light scattering/Intensity 300KHz/Intensity-weight Gaussian Analysis, and the setting values are a temperature of 23°C and a measurement wavelength of 632.8. nm, channel The channel width can be measured as 10 μsec.
前記Ａ－１）グラフト共重合体は、一例として３～２２重量％、好ましくは５～２０重量％、より好ましくは７～１５重量％であり、この範囲内で、耐衝撃性、耐熱度及び流動性に優れ、特に平均面衝撃強度が高いながらも、その標準偏差が減少して大型製品を射出成形することができるだけでなく、ディープブラック色相の実現が可能であり、ゴニオクロミズム（Ｇｏｎｉｏｃｈｒｏｍｉｓｍ）現象の発生を抑制して射出外観品質及び自動車の信頼性評価を満たすという効果がある。 The amount of the graft copolymer A-1) is, for example, 3 to 22% by weight, preferably 5 to 20% by weight, more preferably 7 to 15% by weight, and within this range, impact resistance, heat resistance and It has excellent flowability, especially high average surface impact strength, and its standard deviation is reduced, making it possible not only to injection mold large products, but also to realize deep black hue, and to prevent the phenomenon of goniochromism. This has the effect of suppressing the occurrence of , and satisfying the injection appearance quality and reliability evaluation of automobiles.
本記載において、ゴニオクロミズム（Ｇｏｎｉｏｃｈｒｏｍｉｓｍ）現象は、樹脂間に相溶性が低下して、ペレット又は射出試験片に虹色又は真珠色が現れる現象を指す。前記現象が発現する場合、染料又は顔料の着色性が低下して射出品の外観の色相が不均一であり、顔料又は染料の着色に対して黒色度（Ｌ）の数値が増加し、高黒色の発現が難しいという問題がある。 In this description, the goniochromism phenomenon refers to a phenomenon in which compatibility between resins decreases and a rainbow or pearl color appears in pellets or injection test pieces. When the above phenomenon occurs, the coloring property of the dye or pigment decreases and the hue of the appearance of the injection product becomes uneven, and the value of blackness (L) increases with respect to the coloring of the pigment or dye, resulting in a high black color. There is a problem that it is difficult to express.
前記Ａ－１）グラフト共重合体は、一例として、アクリレート系ゴム３０～６０重量％、芳香族ビニル化合物２０～６０重量％及びビニルシアン化合物５～２０重量％を含んでなるものであり、この範囲内で、耐衝撃性、面衝撃強度及びその標準偏差が改善され、射出外観品質に優れるという効果がある。 The above A-1) graft copolymer contains, for example, 30 to 60% by weight of acrylate rubber, 20 to 60% by weight of aromatic vinyl compound, and 5 to 20% by weight of vinyl cyanide compound; Within this range, the impact resistance, surface impact strength and standard deviation thereof are improved, and the injection appearance quality is excellent.
好ましい例として、前記Ａ－１）グラフト共重合体は、アクリレート系ゴム３５～５５重量％、芳香族ビニル化合物３５～５５重量％及びビニルシアン化合物７～１７重量％を含んでなることができ、この範囲内で、面衝撃強度及びその標準偏差が改善され、射出外観品質に優れるという効果がある。 As a preferred example, the graft copolymer A-1) may include 35 to 55% by weight of acrylate rubber, 35 to 55% by weight of aromatic vinyl compound, and 7 to 17% by weight of vinyl cyanide compound, Within this range, the surface impact strength and its standard deviation are improved, and the injection appearance quality is excellent.
本記載において、ある化合物を含んでなる重合体とは、その化合物を含んで重合された重合体を意味するもので、重合された重合体内の単位体がその化合物に由来する。 In this description, a polymer containing a certain compound means a polymer polymerized containing that compound, and the units in the polymerized polymer are derived from that compound.
前記Ａ－１）グラフト共重合体は、一例として乳化重合で製造されてもよく、この場合、耐衝撃性、耐化学性、耐候性及び着色性に優れるという効果がある。 The graft copolymer A-1) may be produced by emulsion polymerization, for example, and in this case, it has the effect of being excellent in impact resistance, chemical resistance, weather resistance, and colorability.
前記乳化重合は、本発明の属する技術分野で通常行われる乳化グラフト重合方法による場合、特に制限されない。 The emulsion polymerization is not particularly limited as long as it is carried out by an emulsion graft polymerization method commonly performed in the technical field to which the present invention pertains.
本発明のアクリレートは、一例として、アルキル基の炭素数が２～８個であるアルキルアクリレートからなる群から選択された１種以上であってもよく、好ましくは、アルキル基の炭素数が４～８個であるアルキルアクリレートであり、さらに好ましくは、ブチルアクリレートまたはエチルヘキシルアクリレートであってもよい。 The acrylate of the present invention may be, for example, one or more selected from the group consisting of alkyl acrylates in which the alkyl group has 2 to 8 carbon atoms, preferably 4 to 8 carbon atoms in the alkyl group. 8 alkyl acrylate, more preferably butyl acrylate or ethylhexyl acrylate.
本発明の芳香族ビニル化合物は、一例として、スチレン、α－メチルスチレン、ο－メチルスチレン、ρ－メチルスチレン、ｍ－メチルスチレン、エチルスチレン、イソブチルスチレン、ｔ－ブチルスチレン、ο－ブロモスチレン、ρ－ブロモスチレン、ｍ－ブロモスチレン、ο－クロロスチレン、ρ－クロロスチレン、ｍ－クロロスチレン、ビニルトルエン、ビニルキシレン、フルオロスチレン及びビニルナフタレンからなる群から選択される１種以上であってもよく、好ましくはスチレンであってもよい。 Examples of the aromatic vinyl compound of the present invention include styrene, α-methylstyrene, o-methylstyrene, ρ-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, t-butylstyrene, o-bromostyrene, One or more selected from the group consisting of ρ-bromostyrene, m-bromostyrene, o-chlorostyrene, ρ-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene. The material may be styrene, preferably styrene.
本発明のビニルシアン化合物は、一例として、アクリロニトリル、メタクリロニトリル、エチルアクリロニトリル及びイソプロピルアクリロニトリルからなる群から選択された１種以上であってもよく、好ましくはアクリロニトリルである。 The vinyl cyanide compound of the present invention may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile, and isopropylacrylonitrile, and preferably acrylonitrile.
Ａ－２）平均粒径５０～１９９ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体
前記グラフト共重合体のアクリレートゴムは、一例として、平均粒径が５０～１９９ｎｍ、好ましくは７０～１８０ｎｍ、より好ましくは９０～１５０ｎｍであるが、この範囲内で、最終製造される熱可塑性樹脂組成物に、優れた耐候性、着色性、光沢性、衝撃強度及び表面特性を付与することができる。
A-2) Graft copolymer comprising acrylate rubber, aromatic vinyl compound, and vinyl cyanide compound having an average particle size of 50 to 199 nm The acrylate rubber of the graft copolymer has an average particle size of 50 nm to 199 nm, for example. -199nm, preferably 70-180nm, more preferably 90-150nm, but within this range, the final produced thermoplastic resin composition has excellent weather resistance, colorability, gloss, impact strength and surface. Characteristics can be given.
前記Ａ－２）グラフト共重合体は、一例として、１７～４０重量％、好ましくは２０～３５重量％、より好ましくは２５～３０重量％であり、この範囲内で、耐衝撃性、耐熱度及び流動性に優れ、特に平均面衝撃強度が高いながらも、その標準偏差が減少して大型製品を射出成形することができ、ディープブラック色相の実現が可能であると共に、ゴニオクロミズム（Ｇｏｎｉｏｃｈｒｏｍｉｓｍ）現象の発生を抑制して射出外観品質及び自動車の信頼性評価を満たすという効果がある。 The amount of the graft copolymer A-2) is, for example, 17 to 40% by weight, preferably 20 to 35% by weight, more preferably 25 to 30% by weight, and within this range, impact resistance, heat resistance It has excellent fluidity and particularly high average surface impact strength, and its standard deviation is reduced, making it possible to injection mold large products, making it possible to realize deep black hue, and preventing the phenomenon of goniochromism. This has the effect of suppressing the occurrence of , and satisfying the injection appearance quality and reliability evaluation of automobiles.
前記Ａ－２）グラフト共重合体は、一例として、アクリレート系ゴム３０～６０重量％、芳香族ビニル化合物２０～６０重量％及びビニルシアン化合物５～２０重量％を含んでなるものであり、この範囲内で、高黒色の発現に優れ、面衝撃強度の標準偏差が減少して物性が安定化されるという効果がある。 The above A-2) graft copolymer contains, for example, 30 to 60% by weight of acrylate rubber, 20 to 60% by weight of an aromatic vinyl compound, and 5 to 20% by weight of a vinyl cyanide compound; Within this range, there is an effect that the appearance of a high black color is excellent, the standard deviation of the surface impact strength is reduced, and the physical properties are stabilized.
好ましい例として、前記（Ａ－２）グラフト共重合体は、アクリレート系ゴム３５～５５重量％、芳香族ビニル化合物３５～５５重量％及びビニルシアン化合物７～１７重量％を含んでなることができ、この範囲内で、高黒色の発現に優れ、面衝撃強度の標準偏差が減少して物性が安定化されるという効果がある。 As a preferred example, the graft copolymer (A-2) may contain 35 to 55% by weight of acrylate rubber, 35 to 55% by weight of an aromatic vinyl compound, and 7 to 17% by weight of a vinyl cyanide compound. Within this range, there is an effect that the appearance of a high black color is excellent, the standard deviation of the surface impact strength is reduced, and the physical properties are stabilized.
前記Ａ－２）グラフト共重合体は、一例として乳化重合で製造されてもよく、この場合、耐衝撃性、耐化学性、耐候性及び着色性に優れるという効果がある。 The above A-2) graft copolymer may be produced by emulsion polymerization, for example, and in this case, it has the effect of being excellent in impact resistance, chemical resistance, weather resistance, and colorability.
前記乳化重合は、本発明の属する技術分野で通常行われる乳化グラフト重合方法による場合、特に制限されない。 The emulsion polymerization is not particularly limited as long as it is carried out by an emulsion graft polymerization method commonly performed in the technical field to which the present invention pertains.
前記Ａ－１）グラフト共重合体は、一例として、前記Ａ－２）グラフト共重合体よりも少ないかまたは同じ量で含まれてもよく、好ましくは、前記Ａ－１）グラフト共重合体とＡ－２）グラフト共重合体は、重量比が１：１～１：７．５、より好ましくは１：１～１：７、さらに好ましくは１：２～１：４、より一層好ましくは１：２～１：３であってもよく、この範囲内で、面衝撃強度及びその標準偏差が改善されて大型射出成形品に適用可能であり、高黒色の発現が可能であるという利点がある。 The above A-1) graft copolymer may be contained in an amount less than or the same as the above A-2) graft copolymer, and preferably, the above A-1) graft copolymer and the above A-1) graft copolymer. A-2) The graft copolymer has a weight ratio of 1:1 to 1:7.5, more preferably 1:1 to 1:7, even more preferably 1:2 to 1:4, even more preferably 1 :2 to 1:3, and within this range, the surface impact strength and its standard deviation are improved, making it applicable to large injection molded products, and having the advantage of being able to develop a high black color. .
本記載において、ＡとＢの重量比は、Ａ：Ｂの重量比を意味する。 In this description, the weight ratio of A and B means the weight ratio of A:B.
Ｂ）（メタ）アクリル酸アルキルエステル化合物、α－メチルスチレン系化合物及びビニルシアン化合物を含んでなる共重合体
前記Ｂ）共重合体は、一例として３０～６０重量％、好ましくは３５～５５重量％、より好ましくは４２～５４重量％、より一層好ましくは４５～５０重量％であり、この範囲内で、耐衝撃性、耐熱度及び流動性に優れ、特に平均面衝撃強度が高いながらも、その標準偏差が減少して大型製品を射出成形することができ、ディープブラック色相の実現が可能であると共に、ゴニオクロミズム（Ｇｏｎｉｏｃｈｒｏｍｉｓｍ）現象の発生を抑制して射出外観品質及び自動車の信頼性評価を満たすという効果がある。
B) A copolymer comprising a (meth)acrylic acid alkyl ester compound, an α-methylstyrene compound, and a vinyl cyanide compound The above B) copolymer contains, for example, 30 to 60% by weight, preferably 35 to 55% by weight. %, more preferably 42 to 54% by weight, even more preferably 45 to 50% by weight, and within this range, while having excellent impact resistance, heat resistance and fluidity, and particularly high average surface impact strength, As the standard deviation decreases, large products can be injection molded, deep black hue can be realized, and the occurrence of goniochromism phenomenon can be suppressed to improve the appearance quality of injection molding and the reliability evaluation of automobiles. It has the effect of satisfying.
前記Ｂ）共重合体は、一例として、（メタ）アクリル酸アルキルエステル化合物３０～５５重量％、α－メチルスチレン系化合物２５～５０重量％及びビニルシアン化合物１０～３０重量％を含んでなるものであり、この範囲内で、後述するＣ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）との相溶性が改善されてゴニオクロミズム現象が発生しないようにし、射出外観品質に優れるという効果がある。 The copolymer B) contains, for example, 30 to 55% by weight of a (meth)acrylic acid alkyl ester compound, 25 to 50% by weight of an α-methylstyrene compound, and 10 to 30% by weight of a vinyl cyanide compound. Within this range, the compatibility with C) polymethacrylate resin (excluding α-methylstyrene), which will be described later, is improved, the goniochromism phenomenon is prevented from occurring, and the injection appearance quality is excellent. be.
前記Ｂ）共重合体は、好ましくは、（メタ）アクリル酸アルキルエステル化合物３５～５０重量％、α－メチルスチレン系化合物３０～４５重量％及びビニルシアン化合物１２～２７重量％を含んでなるものであってもよく、この範囲内で、後述するＣ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）との相溶性が改善されてゴニオクロミズム現象が発生しないようにし、射出外観に優れるという効果がある。 The copolymer B) preferably contains 35 to 50% by weight of a (meth)acrylic acid alkyl ester compound, 30 to 45% by weight of an α-methylstyrene compound, and 12 to 27% by weight of a vinyl cyanide compound. Within this range, the compatibility with C) polymethacrylate resin (excluding α-methylstyrene), which will be described later, is improved to prevent the occurrence of goniochromism, and the injection appearance is excellent. effective.
前記Ｂ）共重合体は、より好ましくは、（メタ）アクリル酸アルキルエステル化合物４０～４５重量％、α－メチルスチレン系化合物３５～４０重量％及びビニルシアン化合物１７～２２重量％を含んでなるものであってもよく、この範囲内で、後述するＣ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）との相溶性が改善されてゴニオクロミズム現象が発生しないようにし、射出外観に優れるという効果がある。 The copolymer B) more preferably contains 40 to 45% by weight of a (meth)acrylic acid alkyl ester compound, 35 to 40% by weight of an α-methylstyrene compound, and 17 to 22% by weight of a vinyl cyanide compound. Within this range, the compatibility with C) polymethacrylate resin (excluding α-methylstyrene), which will be described later, is improved to prevent the occurrence of goniochromism, and the injection appearance is excellent. There is an effect.
前記Ｂ）共重合体は、一例として重量平均分子量が５０，０００～２００，０００ｇ／ｍｏｌ、好ましくは７０，０００～１５０，０００ｇ／ｍｏｌ、より好ましくは８０，０００～１２０，０００ｇ／ｍｏｌであってもよく、この範囲内で、面衝撃強度に優れ、射出成形性を確保するという効果がある。 For example, the copolymer B) has a weight average molecular weight of 50,000 to 200,000 g/mol, preferably 70,000 to 150,000 g/mol, and more preferably 80,000 to 120,000 g/mol. Within this range, it is effective to have excellent surface impact strength and ensure injection moldability.
本記載において、重量平均分子量は、別途に定義しない限り、ＧＰＣ（ゲルパーミエーションクロマトグラフィー：Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ、ｗａｔｅｒｓ ｂｒｅｅｚｅ）を用いて測定することができ、具体例として、溶出液としてＴＨＦ（テトラヒドロフラン）を用い、ＧＰＣ（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ、ｗａｔｅｒｓ ｂｒｅｅｚｅ）を通じて、標準ＰＳ（標準ポリスチレン：ｓｔａｎｄａｒｄ ｐｏｌｙｓｔｙｒｅｎｅ）試料に対する相対値として測定することができる。このとき、具体的な測定例として、溶媒：ＴＨＦ、カラム温度：４０℃、流速：０．３ｍｌ／分、試料の濃度：２０ｍｇ／ｍｌ、注入量：５μl、カラムモデル：１×ＰＬｇｅｌ １０μｍ ＭｉｎｉＭｉｘ－Ｂ（２５０×４．６ｍｍ）＋１×ＰＬｇｅｌ １０μｍ ＭｉｎｉＭｉｘ－Ｂ（２５０×４．６ｍｍ）＋１×ＰＬｇｅｌ １０μｍ ＭｉｎｉＭｉｘ－Ｂ Ｇｕａｒｄ（５０×４．６ｍｍ）、装置名：Ａｇｉｌｅｎｔ １２００シリーズシステム、屈折率検出器（Ｒｅｆｒａｃｔｉｖｅ ｉｎｄｅｘ ｄｅｔｅｃｔｏｒ）：Ａｇｉｌｅｎｔ Ｇ１３６２ ＲＩＤ、ＲＩ温度：３５℃、データの処理：Ａｇｉｌｅｎｔ ＣｈｅｍＳｔａｔｉｏｎ Ｓ／Ｗ、試験方法（Ｍｎ、Ｍｗ及びＰＤＩ）：ＯＥＣＤ ＴＧ １１８の条件で測定することができる。 In this description, unless otherwise defined, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, THF (tetrahydrofuran) as the eluent. It can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, Waters Breeze). At this time, as a specific measurement example, solvent: THF, column temperature: 40°C, flow rate: 0.3 ml/min, sample concentration: 20 mg/ml, injection volume: 5 μl, column model: 1×PLgel 10 μm MiniMix- B (250 x 4.6 mm) + 1 x PLgel 10 μm MiniMix-B (250 x 4.6 mm) + 1 x PL gel 10 μm MiniMix-B Guard (50 x 4.6 mm), device name: Agilent 1200 series system, refractive index detector (Refractive index detector): Agilent G1362 RID, RI temperature: 35°C, data processing: Agilent ChemStation S/W, test method (Mn, Mw and PDI): Can be measured under the conditions of OECD TG 118.
前記Ｂ）（メタ）アクリル酸アルキルエステル重合体は、一例として、（メタ）アクリル酸メチルエステル、（メタ）アクリル酸エチルエステル、（メタ）アクリル酸プロピルエステル、（メタ）アクリル酸２－エチルヘキシルエステル、（メタ）アクリル酸デシルエステル、及び（メタ）アクリル酸ラウリルエステルからなる群から選択された１種以上であってもよく、好ましくは、（メタ）アクリル酸メチルエステルであるメチルメタクリレートであってもよい。 Examples of the (meth)acrylic acid alkyl ester polymer B) include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, and (meth)acrylic acid 2-ethylhexyl ester. , (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester, preferably methyl methacrylate, which is methyl (meth)acrylic acid ester. Good too.
前記α－メチルスチレン系化合物は、一例として、α－メチルスチレン及びその誘導体からなる群から選択された１種以上であってもよく、この場合に、耐熱性に優れるという効果がある。 The α-methylstyrene compound may be, for example, one or more selected from the group consisting of α-methylstyrene and its derivatives, and in this case, it has the effect of being excellent in heat resistance.
前記α－メチルスチレンの誘導体は、好ましくは、その水素のうち１又は２以上が炭素数１～１０のアルキル基、ハロゲン基などの置換基で置換された化合物であってもよく、より好ましくは、その芳香族環（ａｒｏｍａｔｉｃ ｒｉｎｇ）中の水素のうち１又は２以上が炭素数１～１０のアルキル基、ハロゲン基などの置換基で置換された化合物であってもよい。 The derivative of α-methylstyrene may preferably be a compound in which one or more of its hydrogen atoms is substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms or a halogen group, and more preferably may be a compound in which one or more of the hydrogen atoms in its aromatic ring is substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms or a halogen group.
前記Ｂ）共重合体に含まれたビニルシアン化合物の種類は、本記載のＡ－１）グラフト共重合体に含まれるビニルシアン化合物の種類と同じ範疇内のものであってもよい。 The type of vinyl cyanide compound contained in the copolymer B) may be in the same category as the type of vinyl cyanide compound contained in the graft copolymer A-1) of the present description.
前記Ｂ）共重合体は、一例として、溶液重合、塊状重合、乳化重合または懸濁重合により製造されてもよく、好ましくは塊状重合であってもよく、前記溶液重合、塊状重合、乳化重合及び懸濁重合は、それぞれ本発明の属する技術分野で通常行われる乳化重合及び懸濁重合方法による場合、特に制限されない。 The copolymer B) may be produced by, for example, solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, preferably by bulk polymerization, and may be produced by solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization. Suspension polymerization is not particularly limited as long as it is carried out by emulsion polymerization and suspension polymerization methods, respectively, which are commonly carried out in the technical field to which the present invention pertains.
Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）
前記Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）は、一例として６～３０重量％、好ましくは８～２５重量％、より好ましくは９～２２重量％、より一層好ましくは１０～１６重量％であってもよく、この範囲内で、高黒色の発現性に優れ、溶融流れ指数に優れるため、大型製品の射出が容易であるという効果がある。
C) Polymethacrylate resin (excluding α-methylstyrene)
The polymethacrylate resin (C) (excluding α-methylstyrene) is, for example, 6 to 30% by weight, preferably 8 to 25% by weight, more preferably 9 to 22% by weight, even more preferably 10 to 16% by weight. It may be % by weight, and within this range, there is an effect that large-sized products can be easily injected because the black color is excellent and the melt flow index is excellent.
前記Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）は、好ましくはメタクリレート単量体を５５重量％以上含み、より好ましくは６０重量％以上、最も好ましくは６５重量％以上含み、この範囲内で、高黒色の発現性に優れ、溶融流れ指数に優れるため、大型製品の射出が容易であるという効果がある。 The polymethacrylate resin (C) (excluding α-methylstyrene) preferably contains methacrylate monomer in an amount of 55% by weight or more, more preferably 60% by weight or more, and most preferably 65% by weight or more, within this range. Among them, it has excellent black color development and excellent melt flow index, making it easy to inject large products.
前記メタクリレート単量体は、一例として、アルキル基の炭素数が１～１５であるアルキルメタクリレートであってもよく、具体例として、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート、２－エチルブチルメタクリレート、２－エチルヘキシルメタクリレート及びラウリルメタクリレートからなる群から選択された１種以上であってもよく、好ましくは、炭素数１～４個のアルキル基を含むアルキルメタクリレートであってもよく、より好ましくはメチルメタクリレートであってもよい。 The methacrylate monomer may be, for example, an alkyl methacrylate in which the alkyl group has 1 to 15 carbon atoms, and specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2- It may be one or more selected from the group consisting of ethylhexyl methacrylate and lauryl methacrylate, preferably an alkyl methacrylate containing an alkyl group having 1 to 4 carbon atoms, and more preferably methyl methacrylate. It's okay.
前記Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）は、好ましくはメチルメタクリレート－スチレン－アクリロニトリル共重合体、またはポリメチルメタクリレート樹脂とメチルメタクリレート－スチレン－アクリロニトリル共重合体との混合物であってもよく、この範囲内で、高黒色の発現性に優れ、溶融流れ指数に優れるため、大型製品の射出が容易であるという効果がある。 The polymethacrylate resin (C) (excluding α-methylstyrene) is preferably a methyl methacrylate-styrene-acrylonitrile copolymer or a mixture of a polymethyl methacrylate resin and a methyl methacrylate-styrene-acrylonitrile copolymer. Within this range, it has an effect of being excellent in developing a high black color and having an excellent melt flow index, so that large-sized products can be easily injected.
一例として、前記Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）として、メチルメタクリレート－スチレン－アクリロニトリル共重合体とポリメチルメタクリレートを混合して使用する場合、メチルメタクリレート－スチレン－アクリロニトリル共重合体は、ポリメチルメタクリレート樹脂よりも多いかまたは同じ量で含むことができ、好ましくは、メチルメタクリレート－スチレン－アクリロニトリル共重合体は、ポリメチルメタクリレートよりも多い量で含むことができ、この場合に、流動性、面衝撃強度及びその標準偏差に優れるという効果がある。 As an example, when using a mixture of methyl methacrylate-styrene-acrylonitrile copolymer and polymethyl methacrylate as the above C) polymethacrylate resin (excluding α-methylstyrene), methyl methacrylate-styrene-acrylonitrile copolymer The copolymer may be included in an amount greater than or equal to the polymethyl methacrylate resin, preferably the methyl methacrylate-styrene-acrylonitrile copolymer may be included in an amount greater than the polymethyl methacrylate, in which case , excellent fluidity, surface impact strength, and standard deviation thereof.
具体的な例として、前記熱可塑性樹脂組成物１００重量％中にメチルメタクリレート－スチレン－アクリロニトリル共重合体３～１５重量％及びポリメチルメタクリレート３～１５重量％で含まれてもよく、好ましくは、メチルメタクリレート－スチレン－アクリロニトリル共重合体５～１２重量％及びポリメチルメタクリレート４～１１重量％で使用されてもよく、この場合に、耐熱性、黒色度、及び面衝撃強度及びその標準偏差に優れ、溶融流れ指数に優れるため、大型製品の射出が容易であるという効果がある。 As a specific example, methyl methacrylate-styrene-acrylonitrile copolymer and polymethyl methacrylate may be contained in 3-15% by weight in 100% by weight of the thermoplastic resin composition, preferably, Methyl methacrylate-styrene-acrylonitrile copolymer may be used at 5-12% by weight and polymethyl methacrylate at 4-11% by weight, in which case it has excellent heat resistance, blackness, surface impact strength and its standard deviation. , it has the advantage of being easy to inject large products because of its excellent melt flow index.
前記メチルメタクリレート－スチレン－アクリロニトリル共重合体は、一例として、メチルメタクリレート５５～８２重量％、スチレン１０～３５重量％及びアクリロニトリル１～２０重量％を含んでなり、好ましくは、メチルメタクリレート６０～７７重量％、スチレン１５～３０重量％及びアクリロニトリル１～１５重量％を含んでなり、より好ましくはメチルメタクリレート６７～７２重量％、スチレン２０～２５重量％及びアクリロニトリル５～１０重量％を含んでなり、この範囲内で、溶融流れ指数が改善されて大型製品を容易に射出成形することができ、物性が安定化されるという利点がある。 The methyl methacrylate-styrene-acrylonitrile copolymer includes, for example, 55-82% by weight of methyl methacrylate, 10-35% by weight of styrene, and 1-20% by weight of acrylonitrile, preferably 60-77% by weight of methyl methacrylate. %, 15-30% by weight of styrene and 1-15% by weight of acrylonitrile, more preferably 67-72% by weight of methyl methacrylate, 20-25% by weight of styrene and 5-10% by weight of acrylonitrile. Within this range, there are advantages in that the melt flow index is improved, large products can be easily injection molded, and the physical properties are stabilized.
前記メチルメタクリレート－スチレン－アクリロニトリル共重合体は、一例として重量平均分子量が１００，０００～１８０，０００ｇ／ｍｏｌ、好ましくは１１０，０００～１６０，０００ｇ／ｍｏｌ、より好ましくは１２０，０００ｇ／ｍｏｌ～１４０，０００ｇ／ｍｏｌであってもよく、この範囲内で、面衝撃強度に優れ、射出成形性を確保するという効果がある。 For example, the methyl methacrylate-styrene-acrylonitrile copolymer has a weight average molecular weight of 100,000 to 180,000 g/mol, preferably 110,000 to 160,000 g/mol, and more preferably 120,000 g/mol to 140 g/mol. ,000 g/mol, and within this range, it is effective to have excellent surface impact strength and ensure injection moldability.
前記ポリメチルメタクリレート樹脂は、一例として重量平均分子量が３５，０００～２００，０００ｇ／ｍｏｌであってもよく、好ましくは５０，０００～２００，０００ｇ／ｍｏｌ、より好ましくは８０，０００～１５０，０００ｇ／ｍｏｌであってもよく、この範囲内で、面衝撃強度に優れ、射出成形性を確保するという効果がある。 The polymethyl methacrylate resin may have a weight average molecular weight of 35,000 to 200,000 g/mol, preferably 50,000 to 200,000 g/mol, and more preferably 80,000 to 150,000 g. /mol, and within this range, it is effective to have excellent surface impact strength and ensure injection moldability.
前記ポリメチルメタクリレート樹脂は、一例としてメチルメタクリレート及びメチルアクリレートを含んでなり、好ましくはメチルアクリレートを１～１５重量％、より好ましくは２～７重量％含んでなるものであってもよく、この範囲内で、メチルメタクリレート－スチレン－アクリロニトリル共重合体との相溶性に優れるため、着色性、溶融流れ指数及び機械的物性が向上するという利点がある。 The polymethyl methacrylate resin may contain, for example, methyl methacrylate and methyl acrylate, preferably 1 to 15% by weight, more preferably 2 to 7% by weight of methyl acrylate, within this range. Among them, it has excellent compatibility with the methyl methacrylate-styrene-acrylonitrile copolymer, so it has the advantage of improving colorability, melt flow index, and mechanical properties.
前記Ｃ）ポリメタクリレート樹脂は、一例として、溶液重合、塊状重合、乳化重合または懸濁重合により製造されてもよく、前記溶液重合、塊状重合、乳化重合及び懸濁重合は、それぞれ本発明の属する技術分野で通常行われる乳化重合及び懸濁重合方法による場合、特に制限されない。 The polymethacrylate resin C) may be produced by, for example, solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, and each of the solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization belongs to the present invention. There are no particular limitations as long as emulsion polymerization and suspension polymerization methods commonly used in the technical field are used.
本発明は、好ましくは、前記Ｂ）共重合体と前記Ｃ）ポリメタクリレート樹脂との組み合わせ、より好ましくは、前記Ｂ）共重合体と前記メチルメタクリレート－スチレン－アクリロニトリル共重合体との組み合わせによって、耐熱性、黒色度及び衝撃強度などの機械的物性に優れると共に、面衝撃強度及びその標準偏差がいずれも優れるシナジー効果が発現される。 The present invention preferably provides a combination of the above B) copolymer and the above C) polymethacrylate resin, more preferably a combination of the above B) copolymer and the above methyl methacrylate-styrene-acrylonitrile copolymer, It has excellent mechanical properties such as heat resistance, blackness, and impact strength, as well as excellent surface impact strength and its standard deviation, resulting in a synergistic effect.
添加剤
前記熱可塑性樹脂組成物は、一例として、滑剤、熱安定剤、ＵＶ安定剤及びスリップ剤からなる群から選択された１種以上を含むことができ、この範囲内で、本記載の熱可塑性樹脂組成物本来の物性を低下させないながらも、必要な物性が良好に実現されるという効果がある。
Additive The thermoplastic resin composition may include, for example, one or more selected from the group consisting of a lubricant, a heat stabilizer, a UV stabilizer, and a slip agent, and within this range, the thermoplastic resin composition described herein may contain This has the effect that necessary physical properties can be satisfactorily achieved without degrading the original physical properties of the plastic resin composition.
前記滑剤は、一例として、熱可塑性樹脂組成物の総１００重量部に対して０．１～３重量部、好ましくは０．５～２重量部、より好ましくは０．５～１．５重量部含むことができ、この場合に、衝撃強度及び溶融流れ指数がいずれも優れるという効果がある。 The lubricant is, for example, 0.1 to 3 parts by weight, preferably 0.5 to 2 parts by weight, more preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the thermoplastic resin composition. In this case, the impact strength and melt flow index are both excellent.
前記滑剤は、一例として、エステル系滑剤、金属塩系滑剤、カルボン酸系滑剤、炭化水素系滑剤及びアミド系滑剤からなる群から選択された１種以上であってもよく、好ましくはアミド系滑剤であり、より好ましくはステアルアミド系滑剤であり、さらに好ましくはアルキレンの炭素数が１～１０であるアルキレンビス（ステアルアミド）であり、この場合、樹脂の機械的物性及び熱安定性を低下させないながらも、滑剤本来の効果が良好に発現されるという利点がある。 The lubricant may be, for example, one or more selected from the group consisting of ester lubricants, metal salt lubricants, carboxylic acid lubricants, hydrocarbon lubricants, and amide lubricants, preferably amide lubricants. A stearamide-based lubricant is more preferable, and an alkylene bis(stearamide) in which the alkylene has 1 to 10 carbon atoms is more preferable. This has the advantage that the original effects of the lubricant are well expressed.
本記載において、ステアルアミド系滑剤は、ステアルアミド（ｓｔｅａｒａｍｉｄｅ）及びその水素のうち１以上が他の置換基で置換されたステアルアミド置換体を含むことができる。 In the present description, the stearamide-based lubricant may include stearamide and a stearamide substituted product in which one or more of the hydrogens thereof is substituted with another substituent.
前記エステル系滑剤、金属塩系滑剤、カルボン酸系滑剤、炭化水素系滑剤及びアミド系滑剤は、それぞれ、本発明の属する技術分野で一般的に当該種類の滑剤として使用される物質であれば、特に制限されない。 The ester lubricant, metal salt lubricant, carboxylic acid lubricant, hydrocarbon lubricant, and amide lubricant are each a substance commonly used as the type of lubricant in the technical field to which the present invention pertains, There are no particular restrictions.
前記熱安定剤は、一例として熱可塑性樹脂組成物の総１００重量部に対して０．１～２重量部、好ましくは０．２～１．５重量部であってもよく、この範囲内で、耐熱度が改善されるという効果がある。 The heat stabilizer may be used in an amount of 0.1 to 2 parts by weight, preferably 0.2 to 1.5 parts by weight, based on 100 parts by weight of the thermoplastic resin composition, and within this range. , has the effect of improving heat resistance.
前記熱安定剤は、一例として、フェノール系熱安定剤、ホスファイト系熱安定剤及びチオエーテル系熱安定剤からなる群から選択された１種以上であってもよく、好ましくは、フェノール系熱安定剤及びホスファイト系熱安定剤である。 The thermal stabilizer may be, for example, one or more selected from the group consisting of a phenolic thermal stabilizer, a phosphite thermal stabilizer, and a thioether thermal stabilizer, and preferably a phenolic thermal stabilizer. It is a phosphite-based heat stabilizer.
前記フェノール系熱安定剤は、一例として、テトラキスメチレン３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネートメタン、１，３，５－トリス－（４－ｔ－ブチル－３－ヒドロキシ－２，６－ジメチルベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、及び１，３，５－トリス－（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）－ｓ－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオンからなる群から選択された１種以上であってもよい。 Examples of the phenolic heat stabilizer include tetrakismethylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate methane, and 1,3,5-tris-(4-t-butyl). -3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris-(3,5 It may be one or more selected from the group consisting of -di-t-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)-trione.
前記ホスファイト系熱安定剤は、一例として、トリスノニルフェニルホスファイト、トリス－（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、ビス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスファイト、またはこれらの混合物であってもよい。 Examples of the phosphite-based heat stabilizer include trisnonylphenyl phosphite, tris-(2,4-di-tert-butylphenyl) phosphite, and bis(2,4-di-tert-butylphenyl) pentaerythritol. It may be a diphosphite or a mixture thereof.
前記チオエーテル系熱安定剤は、一例として、ジラウリルチオジプロピオネート、ジミリスチルチオジプロピオネート、ラウリルステアリルチオジプロピオネート、ジステアリルチオジプロピオネート、ジメチルチオジプロピオネート、２－メルカプトベンゾイミダゾール、フェノチアジン、オクタデシルチオグリコレート、ブチルチオグリコレート、オクチルチオグリコレート及びチオクレゾールからなる群から選択された１種以上であってもよい。 Examples of the thioether heat stabilizer include dilaurylthiodipropionate, dimyristylthiodipropionate, laurylstearylthiodipropionate, distearylthiodipropionate, dimethylthiodipropionate, and 2-mercaptobenzimidazole. , phenothiazine, octadecylthioglycolate, butylthioglycolate, octylthioglycolate, and thiocresol.
前記ＵＶ安定剤は、一例として、熱可塑性樹脂組成物の総１００重量部に対して０．１～３重量部、好ましくは０．５～１．５重量部であってもよく、この場合、耐候性が改善されるという効果がある。 The UV stabilizer may be used in an amount of, for example, 0.1 to 3 parts by weight, preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the thermoplastic resin composition; in this case, This has the effect of improving weather resistance.
前記ＵＶ安定剤は、一例として、ヒンダードアミン系ＵＶ安定剤（ｈｉｎｄｅｒｅｄ ａｍｉｎｅ ｌｉｇｈｔ ｓｔａｂｉｌｉｚｅｒ、ＨＡＬＳ）であってもよく、好ましくは、１，１－ビス（２，２，６，６－テトラメチル－４－ピペリジル）スクシナート、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セバケート、ビス（１－オクチルオキシ－２，２，６，６－テトラメチル－４－ピペリジル）セバケート、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）－Ｎ－ブチル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルマロネート、１－（２－ヒドロキシエチル）－２，２，６，６－テトラメチル－４－ヒドロキシピペリジンとコハク酸との縮合生成物、Ｎ，Ｎ’－ビス（２，２，６，６－テトラメチル－４－ピペリジル）ヘキサメチレンジアミンと４－ｔｅｒｔ－オクチルアミノ－２，６－ジ－クロロ－１，３，５－トリアジンとの線状又は環状縮合生成物、トリス（２，２，６，６－テトラメチル－４－ピペリジル）ニトリロトリアセテート、テトラキス（２，２，６，６－テトラメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、１，１’－（１，２－エタンジイル）－ビス（３，３，５，５－テトラメチルピペラジノン）、４－ベンゾイル－２，２，６，６－テトラメチルピペリジン、４－ステアリルオキシ－２，２，６，６－テトラメチルピペリジン、Ｎ，Ｎ’－ビス（２，２，６，６－テトラメチル－４－ピペリジル）ヘキサメチレンジアミンと４－モルホリノ－２，６－ジクロロ－１，３，５－トリアジンとの線状又は環状縮合生成物、７，７，９，９－テトラメチル－２－シクロウンデシル－１－オキサ－３，８－ジアザ－４－オキソスピロ－［４，５］デカンとエピクロロヒドリンとの反応生成物、及びポリ［［６－（１，１，３，３－テトラメチルブチル）アミノ］－１，３，５－トリアジン－２，４－ジイル］［（２，２，６，６－テトラメチル－４－ピペリジニル）イミノ］－１，６－ヘキサンジイル［（２，２，６，６－テトラメチル－４－ピペリジニル）イミノ］からなる群から選択された１種以上であってもよい。 The UV stabilizer may be, for example, a hindered amine light stabilizer (HALS), preferably 1,1-bis(2,2,6,6-tetramethyl-4- piperidyl) succinate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy- 2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-N-butyl-3,5-di-tert-butyl- 4-Hydroxybenzylmalonate, condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N,N'-bis(2,2 ,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-triazine, tris( 2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1 , 1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy- 2,2,6,6-tetramethylpiperidine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1, Linear or cyclic condensation product with 3,5-triazine, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5 ] The reaction product of decane and epichlorohydrin, and poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][ (2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino] There may be one or more types.
前記ＵＶ安定剤は、より好ましくは、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート（Ｂｉｓ（２，２，６，６－ｔｅｔｒａｍｅｔｈｙｌ－４－ｐｉｐｅｒｉｄｙｌ）ｓｅｂａｃａｔｅ）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール（２－（２Ｈ－ｂｅｎｚｏｔｒｉａｚｏｌ－２－ｙｌ）－４－（１，１，３，３－ｔｅｔｒａｍｅｔｈｙｌｂｕｔｙｌ）ｐｈｅｎｏｌ）、ポリ［［６－（１，１，３，３－テトラメチルブチル）アミノ］－１，３，５－トリアジン－２，４－ジイル］［（２，２，６，６－テトラメチル－４－ピペリジニル）イミノ］－１，６－ヘキサンジイル［（２，２，６，６－テトラメチル－４－ピペリジニル）イミノ］、またはこれらの混合物であってもよく、より一層好ましくは、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート（Ｂｉｓ（２，２，６，６－ｔｅｔｒａｍｅｔｈｙｌ－４－ｐｉｐｅｒｉｄｙｌ）、ポリ［［６－（１，１，３，３－テトラメチルブチル）アミノ］－１，３，５－トリアジン－２，４－ジイル］［（２，２，６，６－テトラメチル－４－ピペリジニル）イミノ］－１，６－ヘキサンジイル［（２，２，６，６－テトラメチル－４－ピペリジニル）イミノ］、またはこれらの混合物であってもよく、このような場合、衝撃強度及び流動性を阻害しないと共に、耐候性を大きく改善させるという利点がある。 The UV stabilizer is more preferably Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (2-(2H-benzotriazol-2-yl)-4-(1,1,3,3 -tetramethylbutyl)phenol), poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6 -tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino], or a mixture thereof, and is even more preferable. is bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Bis(2,2,6,6-tetramethyl-4-piperidyl), poly[[6-(1,1,3, 3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[ (2,2,6,6-tetramethyl-4-piperidinyl)imino] or a mixture thereof; in such a case, it does not impede impact strength and fluidity and greatly improves weather resistance. There is an advantage.
前記スリップ剤は、一例として熱可塑性樹脂組成物の総１００重量部に対して０．１～３重量部、好ましくは０．５～２重量部であってもよく、この範囲内で、耐摩擦性が改善されるという効果がある。 The slip agent may be used in an amount of 0.1 to 3 parts by weight, preferably 0.5 to 2 parts by weight, based on a total of 100 parts by weight of the thermoplastic resin composition, and within this range, the amount of the slip agent It has the effect of improving sex.
本記載において、滑剤は、射出加工時の成形性（加工性）を改善させるために使用され、スリップ剤は、射出成形後の完成された製品の表面特性を向上させるために使用されるものを指す。 In this description, lubricants are used to improve moldability (processability) during injection processing, and slip agents are those used to improve the surface properties of the finished product after injection molding. Point.
前記スリップ剤は、一例としてポリエステル変性シロキサンであってもよく、この場合、熱可塑性樹脂組成物との相溶性に優れるという利点がある。 The slip agent may be, for example, a polyester-modified siloxane, which has the advantage of excellent compatibility with the thermoplastic resin composition.
具体的に前記ポリエステル変性シロキサンは、主鎖がポリジメチルシロキサンであり、前記ポリジメチルシロキサンの有機基（ｏｒｇａｎｉｃ ｇｒｏｕｐ）がポリエステルで置換されて、ポリジメチルシロキサンを主鎖とし、ポリエステルを側鎖として含むことができ、この場合、熱可塑性樹脂組成物との相溶性がさらに向上して組成物の物性バランスが高く維持されながらも、耐摩擦性がさらに改善されるという利点を提供する。 Specifically, the polyester-modified siloxane has a main chain of polydimethylsiloxane, an organic group of the polydimethylsiloxane is substituted with polyester, and contains polydimethylsiloxane as the main chain and polyester as a side chain. In this case, the compatibility with the thermoplastic resin composition is further improved, and while the physical property balance of the composition is maintained at a high level, the abrasion resistance is further improved.
前記ポリエステル変性シロキサンは、末端にヒドロキシ基を有するポリエステル変性シロキサンであってもよく、この場合、熱可塑性樹脂組成物との相溶性がさらに優れるため、全体的な物性バランスを高く維持しながらも耐摩擦性を大きく向上させることができる。 The polyester-modified siloxane may be a polyester-modified siloxane having a hydroxyl group at the end. In this case, the compatibility with the thermoplastic resin composition is even better, so that the polyester-modified siloxane has excellent durability while maintaining a high overall balance of physical properties. Frictional properties can be greatly improved.
前記ポリエステル変性シロキサンは、融点が、一例として５０～５５℃、好ましくは５２～５５℃であってもよく、この範囲内で、前記熱可塑性樹脂組成物とのコンパウンディングが容易であるという利点がある。 The polyester-modified siloxane may have a melting point of, for example, 50 to 55°C, preferably 52 to 55°C, and within this range, it has the advantage that compounding with the thermoplastic resin composition is easy. be.
本記載において、融点は、ＴＡ社で製造した示差走査熱量計（ＤＳＣ：Ｄｉｆｆｅｒｅｎｔｉａｌ Ｓｃａｎｎｉｎｇ Ｃａｌｏｒｉｍｅｔｅｒ ２９２０）を用いて測定できる。具体的な測定例として、融点は、ＤＳＣを温度０℃で平衡に達するようにした後、１分当たり２０℃ずつ増加させて１８０℃まで上げた後、１分当たり２０℃ずつ減少させて－６０℃まで下げた後、１分当たり１０℃ずつ増加させて１８０℃まで温度を増加させる方法により測定できる。ここで、融点は、二番目の温度が上昇する間、吸熱曲線の頂点領域を取って得られる。 In this description, the melting point can be measured using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 2920) manufactured by TA. As a specific measurement example, the melting point is determined by allowing the DSC to reach equilibrium at a temperature of 0°C, increasing it by 20°C per minute to 180°C, and then decreasing it by 20°C per minute. It can be measured by a method in which the temperature is lowered to 60°C and then increased by 10°C per minute up to 180°C. Here, the melting point is obtained by taking the apex area of the endothermic curve during the second temperature increase.
前記ポリエステル変性シロキサンはペレット状であることを特徴とすることができ、この場合、熱可塑性樹脂組成物とのコンパウンディングが容易であるため生産性を向上させることができる。 The polyester-modified siloxane can be characterized in that it is in the form of pellets, and in this case, compounding with the thermoplastic resin composition is easy, so productivity can be improved.
前記熱可塑性樹脂組成物は、必要に応じて選択的に染料、顔料、難燃剤及び無機充填剤からなる群から選択された１種以上を、熱可塑性樹脂組成物１００重量部に対して、それぞれ０．０１～５重量部、好ましくは０．０５～３重量部、より好ましくは０．１～２重量部、より一層好ましくは０．５～１重量部さらに含むことができ、この範囲内で、本記載の熱可塑性樹脂組成物本来の物性を低下させないながらも、必要な物性が良好に実現されるという効果がある。 The thermoplastic resin composition may optionally contain one or more selected from the group consisting of dyes, pigments, flame retardants, and inorganic fillers, respectively, based on 100 parts by weight of the thermoplastic resin composition. 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, even more preferably 0.5 to 1 part by weight, and within this range This has the effect that necessary physical properties can be satisfactorily achieved without reducing the inherent physical properties of the thermoplastic resin composition described herein.
熱可塑性樹脂組成物
本発明の熱可塑性樹脂組成物は、好ましくは、ＩＳＯ ６６０３－２に準拠して、速度４．４ｍ／ｓ下で試験片の厚さ２．０ｍｍで最大荷重エネルギーを１０回測定した平均面衝撃強度が２２Ｊ以上、より好ましくは２３Ｊ以上、さらに好ましくは２３～２７Ｊ、より一層好ましくは２４～２７Ｊであってもよく、このとき、その標準偏差は、好ましくは６．５以下、より好ましくは６以下、さらに好ましくは５以下、より一層好ましくは３～５であってもよく、この範囲内で、自動車外装材において求められる主要な信頼性評価を満たすという効果がある。
Thermoplastic Resin Composition The thermoplastic resin composition of the present invention preferably has a maximum load energy of 10 times at a speed of 4.4 m/s and a test piece thickness of 2.0 mm in accordance with ISO 6603-2. The measured average surface impact strength may be 22 J or more, more preferably 23 J or more, still more preferably 23 to 27 J, even more preferably 24 to 27 J, in which case the standard deviation thereof is preferably 6.5 or less. , more preferably 6 or less, still more preferably 5 or less, and even more preferably 3 to 5. Within this range, there is an effect of satisfying the main reliability evaluation required for automobile exterior materials.
また、前記熱可塑性樹脂組成物は、好ましくはＩＳＯ １７９に準拠して、ノッチ付き試験片で測定したシャルピー衝撃強度（２３℃）が９ｋＪ／ｍ２以上、より好ましくは１０ｋＪ／ｍ２～１７ｋＪ／ｍ２、さらに好ましくは１２～１５ｋＪ／ｍ２であってもよく、この範囲内で、物性バランスに優れ、大型射出成形品に求められる衝撃強度を満たす。 Further, the thermoplastic resin composition preferably has a Charpy impact strength (23°C) of 9 kJ/m 2 or more, more preferably 10 kJ/m 2 to 17 kJ/ m 2 , more preferably 12 to 15 kJ/m 2 , and within this range, the physical property balance is excellent and the impact strength required for large injection molded products is satisfied.
また、前記熱可塑性樹脂組成物は、好ましくはＩＳＯ １１３３に準拠して、２２０℃、１０ｋｇ下で測定した溶融流れ指数が５．５ｇ／１０分以上、より好ましくは６～１０ｇ／１０分、さらに好ましくは６～９ｇ／１０分であってもよく、この範囲内で、流れ性に優れるため、大型製品の射出成形が容易であるという利点がある。 The thermoplastic resin composition preferably has a melt flow index of 5.5 g/10 minutes or more, more preferably 6 to 10 g/10 minutes, measured at 220° C. and under 10 kg according to ISO 1133. Preferably, it may be 6 to 9 g/10 minutes, and within this range, there is an advantage that injection molding of large products is easy due to excellent flowability.
前記熱可塑性樹脂組成物は、好ましくはＩＳＯ ７５／Ｂｅに準拠して１．８ＭＰａ下で測定した熱変形温度が７７℃以上、より好ましくは７８～８５℃、さらに好ましくは８０～８５℃であってもよく、この範囲内で、全ての物性バランスに優れるという効果がある。 The thermoplastic resin composition preferably has a heat distortion temperature of 77°C or higher, more preferably 78 to 85°C, even more preferably 80 to 85°C, as measured under 1.8 MPa in accordance with ISO 75/Be. Within this range, an excellent balance of all physical properties can be obtained.
前記熱可塑性樹脂組成物は、好ましくは、熱可塑性樹脂組成物１００重量部に対して、カーボンブラック顔料としてＢＫ５６（ムイル化成社製）３重量部及びＢＫ５７（ムイル化成社製）０．５重量部を含んで、射出温度２４０℃及び金型温度６０℃で１００×１００×３ｍｍのサイズの試験片を製造し、カラーメータ（Ｃｏｌｏｒｍｅｔｅｒ）を用いてＳＣＩモードで測定した黒色度（Ｌ；顔料）が２６．５以下、より好ましくは２０～２６．５、さらに好ましくは２２～２６．２であってもよく、この範囲内で、全ての物性バランスに優れると共に、ディープブラック色相を実現するという効果がある。 The thermoplastic resin composition preferably contains 3 parts by weight of BK56 (manufactured by Muil Kasei Co., Ltd.) and 0.5 parts by weight of BK57 (manufactured by Muil Kasei Co., Ltd.) as carbon black pigments based on 100 parts by weight of the thermoplastic resin composition. A test piece with a size of 100 x 100 x 3 mm was manufactured at an injection temperature of 240 °C and a mold temperature of 60 °C, and the blackness (L; pigment) was measured in SCI mode using a color meter. It may be 26.5 or less, more preferably 20 to 26.5, and even more preferably 22 to 26.2. Within this range, it is possible to achieve an excellent balance of all physical properties and to achieve a deep black hue. be.
前記熱可塑性樹脂組成物は、好ましくは、熱可塑性樹脂組成物１００重量部に対して、染料としてＢＫ３９（ムイル化成社製）０．６重量部を含んで、射出温度２４０℃及び金型温度６０℃で１００×１００×３ｍｍのサイズの試験片を製造し、カラーメータ（Ｃｏｌｏｒｍｅｔｅｒ）を用いてＳＣＩモードで測定した黒色度（Ｌ；染料）が２６以下、より好ましくは２０～２６、さらに好ましくは２３～２６であってもよく、この範囲内で、全ての物性バランスに優れると共に、ディープブラック色相を実現するという効果がある。 The thermoplastic resin composition preferably contains 0.6 parts by weight of BK39 (manufactured by Muil Kasei Co., Ltd.) as a dye with respect to 100 parts by weight of the thermoplastic resin composition, and the injection temperature is 240°C and the mold temperature is 60°C. A test piece with a size of 100 x 100 x 3 mm is prepared at It may be from 23 to 26, and within this range, it is effective in achieving an excellent balance of all physical properties and realizing a deep black hue.
前記熱可塑性樹脂組成物は、好ましくはＩＳＯ ５２７に準拠して測定した引張強度が４４ＭＰａ以上、より好ましくは４５ＭＰａ以上、さらに好ましくは４５～５５ＭＰａであってもよく、この範囲内で、全ての物性バランスに優れるという効果がある。 The thermoplastic resin composition preferably has a tensile strength of 44 MPa or more, more preferably 45 MPa or more, and even more preferably 45 to 55 MPa, as measured in accordance with ISO 527, and within this range, all physical properties are It has the effect of providing excellent balance.
前記熱可塑性樹脂組成物は、一例として、熱可塑性樹脂組成物から射出成形された試験片の表面を目視で観察してゴニオクロミズム現象が発生しなかったものであってもよく、この場合、表面品質に優れるという効果がある。 For example, the thermoplastic resin composition may be one in which no goniochromism phenomenon occurs when visually observing the surface of a test piece injection-molded from the thermoplastic resin composition. It has the effect of superior quality.
以下では、本発明の熱可塑性樹脂組成物の製造方法及びその組成物を含む成形品に関して説明する。本発明の熱可塑性樹脂組成物の製造方法及びその組成物を含む成形品を説明するにおいて、上述した熱可塑性樹脂組成物の内容をすべて含む。 Below, a method for producing a thermoplastic resin composition of the present invention and a molded article containing the composition will be explained. In explaining the method for producing a thermoplastic resin composition of the present invention and a molded article containing the composition, all the contents of the above-mentioned thermoplastic resin composition are included.
熱可塑性樹脂組成物の製造方法
本記載の熱可塑性樹脂組成物の製造方法は、Ａ－１）平均粒径２００～４００ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体３～２２重量％と、Ａ－２）平均粒径５０～１９９ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体１７～４０重量％と、Ｂ）（メタ）アクリル酸アルキルエステル化合物、α－メチルスチレン系化合物及びビニルシアン化合物を含んでなる共重合体３０～５７重量％と、Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを除く）６～３０重量と；を混合した後、２００～３００℃下で１０～１００ファイ規格で押出混練機を用いて熱可塑性樹脂組成物を製造するステップを含み；前記熱可塑性樹脂組成物は、ＩＳＯ ６６０３－２に準拠して、速度４．４ｍ／ｓ下で試験片の厚さ２．０ｍｍで最大荷重エネルギーを１０回測定した平均面衝撃強度が２２Ｊ／ｍｍ以上であり、標準偏差が６．５以下であることを特徴とする。このような場合、耐衝撃性、耐熱度及び流動性に優れるため大型製品を射出成形することができ、ディープブラック色相の実現が可能であると共に、ゴニオクロミズム（Ｇｏｎｉｏｃｈｒｏｍｉｓｍ）現象の発生を抑制して射出外観品質及び自動車の信頼性評価を満たすという効果がある。
Method for producing a thermoplastic resin composition The method for producing a thermoplastic resin composition described herein includes A-1) a graft comprising an acrylate rubber having an average particle size of 200 to 400 nm, an aromatic vinyl compound, and a vinyl cyanide compound; 3 to 22% by weight of a copolymer, A-2) 17 to 40% by weight of a graft copolymer comprising an acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound having an average particle size of 50 to 199 nm; ) 30 to 57% by weight of a copolymer comprising a (meth)acrylic acid alkyl ester compound, an α-methylstyrene compound, and a vinyl cyanide compound, and C) a polymethacrylate resin (excluding α-methylstyrene) 6 ~30% by weight; and then manufacturing a thermoplastic resin composition using an extrusion kneader at 200~300°C with a standard of 10~100 phi; the thermoplastic resin composition conforms to ISO 6603 -2, the average surface impact strength obtained by measuring the maximum load energy 10 times with a test piece thickness of 2.0 mm at a speed of 4.4 m/s is 22 J/mm or more, and the standard deviation is 6.5. It is characterized by the following: In such cases, large products can be injection molded due to its excellent impact resistance, heat resistance, and fluidity, and it is possible to achieve a deep black hue and suppress the occurrence of the goniochromism phenomenon. It has the effect of satisfying injection appearance quality and automobile reliability evaluation.
前記混練及び押出は、一例として、一軸押出機、二軸押出機、またはバンバリーミキサーを介して行われてもよく、この場合、組成物が均一に分散して相溶性に優れるという効果がある。 The kneading and extrusion may be performed using, for example, a single-screw extruder, a twin-screw extruder, or a Banbury mixer. In this case, the composition is uniformly dispersed and has excellent compatibility.
前記混練及び押出は、一例としてバレル温度２００～３００℃、好ましくは２１０～２８０℃、より好ましくは２２０～２５０℃の範囲内で行われてもよく、この場合、単位時間当たりの処理量が適切であり、かつ十分な溶融混練が可能となり得、樹脂成分の熱分解などの問題を引き起こさないという効果がある。 The kneading and extrusion may be carried out at a barrel temperature of 200 to 300°C, preferably 210 to 280°C, more preferably 220 to 250°C, and in this case, the throughput per unit time is appropriate. In addition, sufficient melt-kneading is possible, and there is an effect that problems such as thermal decomposition of the resin component do not occur.
前記混練及び押出は、一例として、スクリュー回転数が１００～５００ｒｐｍ、１５０～４００ｒｐｍ、１００～３５０ｒｐｍ、２００～３１０ｒｐｍ、好ましくは２５０～３５０ｒｐｍである条件下で行われてもよく、この場合、単位時間当たりの処理量が適切であるため、工程効率に優れながらも、過度の切断を抑制するという効果がある。 The kneading and extrusion may be carried out, for example, under conditions where the screw rotation speed is 100 to 500 rpm, 150 to 400 rpm, 100 to 350 rpm, 200 to 310 rpm, preferably 250 to 350 rpm, and in this case, the unit time Since the per-processing amount is appropriate, it has the effect of suppressing excessive cutting while being excellent in process efficiency.
成形品
本記載の成形品は、一例として、本記載の熱可塑性樹脂組成物を含むことができ、この場合、耐衝撃性、耐熱度及び流動性に優れるため大型製品を射出成形することができ、ディープブラック色相の実現が可能であると共に、ゴニオクロミズム（Ｇｏｎｉｏｃｈｒｏｍｉｓｍ）現象の発生を抑制して射出外観品質及び自動車の信頼性評価を満たすという効果がある。
Molded product The molded product described herein may include, for example, the thermoplastic resin composition described herein, and in this case, large products can be injection molded due to its excellent impact resistance, heat resistance, and fluidity. , it is possible to realize a deep black hue, and the occurrence of the goniochromism phenomenon is suppressed, thereby satisfying the injection appearance quality and reliability evaluation of automobiles.
前記成形品は、一例として自動車外装材であってもよく、具体的にラジエーターグリルのような大型射出成形品であってもよく、この場合、本記載の熱可塑性樹脂組成物によって、市場で求められる品質以上の高品質で提供可能であるという利点がある。 The molded product may be, for example, an automobile exterior material, or specifically a large injection molded product such as a radiator grill. It has the advantage that it can be provided with a higher quality than that currently available.
以下、本発明の理解を助けるために好ましい実施例を提示するが、以下の実施例は、本発明を例示するものに過ぎず、本発明の範疇及び技術思想の範囲内で様々な変更及び修正が可能であることは当業者にとって明らかであり、このような変更及び修正が添付の特許請求の範囲に属することも当然である。 Hereinafter, preferred embodiments will be presented to help understand the present invention. However, the following embodiments are merely illustrative of the present invention, and various changes and modifications may be made within the scope of the scope and technical idea of the present invention. It will be obvious to those skilled in the art that variations are possible and such changes and modifications are within the scope of the appended claims.
［実施例］
（Ａ－１）ＡＳＡグラフト共重合体：平均粒径３００ｎｍのブチルアクリレートゴム４０重量％、スチレン４３．８重量％、アクリロニトリル１６．２重量％
（Ａ－２）ＡＳＡグラフト共重合体：平均粒径１３０ｎｍのブチルアクリレートゴム５０重量％、スチレン３６．５重量％、アクリロニトリル１３．５重量％
（Ａ－３）ＡＳＡグラフト共重合体：平均粒径４５０ｎｍのブチルアクリレートゴム５０重量％、スチレン３６．５重量％、アクリロニトリル１３．５重量％
（Ｂ－１）塊状重合方式のＭＭＡ系耐熱ＳＡＮ樹脂：メチルメタクリレート４５重量％、α－メチルスチレン３６重量％、アクリロニトリル１９重量％
（Ｂ－２）塊状重合方式の耐熱ＳＡＮ樹脂：α－メチルスチレン７２重量％、アクリロニトリル２８重量％
（Ｂ－３）塊状重合方式のＰＭＩ耐熱樹脂：Ｄｅｎｋａ社のＭＳＮＪ
（Ｃ－１）ＭＭＡ－ＳＡＮ樹脂：メタクリレート７１重量％、スチレン２２重量％、アクリロニトリル７重量％
（Ｃ－２）懸濁重合方式のＰＭＭＡ樹脂：ポリメチルメタクリレート樹脂（重量平均分子量１０１，０００ｇ／ｍｏｌ）
（Ｄ）滑剤：エチレンビスステアロアミド（ＥＢＡ、ＳＵＮＫＯＯ社製）
（Ｅ－１）熱安定剤：ＩＲ１０７６（ＢＡＳＦ社製）
（Ｅ－２）熱安定剤：ＩＦ１６８（ＢＡＳＦ社製）
（Ｆ－１）ＵＶ安定剤：Ｔｉｎ－７００（ＢＡＳＦ社製）
（Ｆ－２）ＵＶ安定剤：Ｃｈｉｍａｓｓｏｒｂ－９４４（グローバルプランニング社製）
（Ｇ）スリップ剤：Ｈ－Ｓｉ ６４４１Ｐ（ＥＶＯＮＩＫ社製）
[Example]
(A-1) ASA graft copolymer: 40% by weight of butyl acrylate rubber with an average particle size of 300 nm, 43.8% by weight of styrene, 16.2% by weight of acrylonitrile.
(A-2) ASA graft copolymer: 50% by weight of butyl acrylate rubber with an average particle size of 130 nm, 36.5% by weight of styrene, 13.5% by weight of acrylonitrile.
(A-3) ASA graft copolymer: 50% by weight of butyl acrylate rubber with an average particle size of 450 nm, 36.5% by weight of styrene, 13.5% by weight of acrylonitrile.
(B-1) Bulk polymerization type MMA heat-resistant SAN resin: 45% by weight of methyl methacrylate, 36% by weight of α-methylstyrene, 19% by weight of acrylonitrile
(B-2) Heat-resistant SAN resin using bulk polymerization method: α-methylstyrene 72% by weight, acrylonitrile 28% by weight
(B-3) PMI heat-resistant resin using bulk polymerization method: Denka's MSNJ
(C-1) MMA-SAN resin: 71% by weight of methacrylate, 22% by weight of styrene, 7% by weight of acrylonitrile
(C-2) PMMA resin using suspension polymerization method: polymethyl methacrylate resin (weight average molecular weight 101,000 g/mol)
(D) Lubricant: Ethylene bisstearamide (EBA, manufactured by SUNKOO)
(E-1) Heat stabilizer: IR1076 (manufactured by BASF)
(E-2) Heat stabilizer: IF168 (manufactured by BASF)
(F-1) UV stabilizer: Tin-700 (manufactured by BASF)
(F-2) UV stabilizer: Chimassorb-944 (manufactured by Global Planning Co., Ltd.)
(G) Slip agent: H-Si 6441P (manufactured by EVONIK)
実施例１～６及び比較例１～１１
それぞれ、下記表１～表３に記載された成分及び含量を、押出機（ＳＭ Ｔｗｉｎ ｓｃｒｅｗ ｅｘｔｒｕｄｅｒ、２５Φ）にて押出温度２４０℃、供給量（Ｆｅｅｄ ｒａｔｅ） ２０ｋｇ／ｈｒ、スクリュー回転数（Ｓｃｒｅｗ ｓｐｅｅｄ）３００ｒｐｍ下で混練及び押出してペレットを製造した。製造されたペレットを用いて溶融指数を測定した。また、製造されたペレットをもって、射出機（ＥＮＧＥＬ社、１２０ＭＴ）にて射出温度２４０℃、金型温度６０℃及び射出速度３０ｍｍ／分の条件下で射出試験片を作製した。
Examples 1 to 6 and Comparative Examples 1 to 11
The components and contents listed in Tables 1 to 3 below were extruded using an extruder (SM Twin screw extruder, 25Φ) at an extrusion temperature of 240°C, a feed rate of 20 kg/hr, and a screw speed. ) Pellets were prepared by kneading and extruding at 300 rpm. The melting index was measured using the pellets produced. In addition, injection test pieces were prepared using the produced pellets using an injection machine (ENGEL, 120MT) under conditions of an injection temperature of 240°C, a mold temperature of 60°C, and an injection speed of 30 mm/min.
［試験例］
前記実施例１～６及び比較例１～１１で製造されたペレット及び射出試験片の特性を下記の方法により測定し、その結果を下記の表１～表３に示した。
[Test example]
The properties of the pellets and injection test pieces produced in Examples 1 to 6 and Comparative Examples 1 to 11 were measured by the following methods, and the results are shown in Tables 1 to 3 below.
＊シャルピー衝撃強度（ｋＪ／ｍ２）：ノッチ付き試験片（厚さ４ｍｍ）を用いてＩＳＯ １７９／１ｅＡに準拠して２３℃で測定した。 *Charpy impact strength (kJ/m 2 ): Measured at 23° C. in accordance with ISO 179/1eA using a notched test piece (thickness 4 mm).
＊溶融流れ指数（Ｍｅｌｔ ｆｌｏｗ ｒａｔｅ、ＭＦＲ；ｇ／１０分）：製造されたペレットをＩＳＯ １１３３に準拠して２２０℃、１０ｋｇの条件下で測定した。 *Melt flow rate (MFR; g/10 minutes): The produced pellets were measured under the conditions of 220° C. and 10 kg in accordance with ISO 1133.
＊引張強度（Ｔｅｎｓｉｌｅ ｓｔｒｅｎｇｔｈ：ＭＰａ）：ＩＳＯ ５２７に準拠して測定した。 *Tensile strength (MPa): Measured in accordance with ISO 527.
＊熱変形温度（Ｈｅａｒ ｄｅｆｌｅｃｔｉｏｎ ｔｅｍｐｅｒａｔｕｒｅ、ＨＤＴ；℃）：ＩＳＯ ７５／Ｂｅに準拠して１．８ＭＰａ下で測定した。 *Hear deflection temperature (HDT; °C): Measured under 1.8 MPa in accordance with ISO 75/Be.
＊平均面衝撃強度（Ｍｕｌｔｉ－ａｘｉａｌ ｉｍｐａｃｔ ｓｔｒｅｎｇｔｈ；Ｊ）及び面衝撃強度の標準偏差：ＩＳＯ ６６０３－２に準拠して、速度４．４ｍ／ｓ下で試験片の厚さ２．０ｍｍで最大荷重エネルギーを１０回測定して平均値及び標準偏差値を求めた。 *Multi-axial impact strength (J) and standard deviation of surface impact strength: Maximum load at a speed of 4.4 m/s and a specimen thickness of 2.0 mm, according to ISO 6603-2. The energy was measured 10 times and the average value and standard deviation value were determined.
＊黒色度（Ｌ）：１００×１００×３ｍｍのサイズの射出された顔料試験片及び染料試験片をもって、カラーメータ（Ｃｏｌｏｒｍｅｔｅｒ）を用いてＳＣＩモードで黒色度（Ｌ）を測定した。 *Blackness (L): The blackness (L) was measured in SCI mode using a colormeter using an injected pigment test piece and dye test piece with a size of 100 x 100 x 3 mm.
黒色度（Ｌ）の値が低いほど、高黒色が発現されたものである。 The lower the blackness (L) value is, the higher the blackness is expressed.
顔料試験片は、熱可塑性樹脂組成物１００重量部に対して、カーボンブラック顔料としてＢＫ５６（ムイル化成社製）３重量部及びＢＫ５７（ムイル化成社製）０．５重量部を混練及び押出してペレットを製造した後、射出温度２４０℃及び金型温度６０℃で射出して１００×１００×３ｍｍのサイズの顔料試験片を製造した。 The pigment test piece was made into pellets by kneading and extruding 3 parts by weight of BK56 (manufactured by Muil Kasei Co., Ltd.) and 0.5 parts by weight of BK57 (manufactured by Muiru Kasei Co., Ltd.) as carbon black pigments with respect to 100 parts by weight of a thermoplastic resin composition. After manufacturing, injection was performed at an injection temperature of 240° C. and a mold temperature of 60° C. to manufacture a pigment test piece with a size of 100×100×3 mm.
染料試験片は、熱可塑性樹脂組成物１００重量部に対して、染料としてＢＫ３９（ムイル化成社製）０．６重量部を混練及び押出してペレットを製造した後、射出温度２４０℃及び金型温度６０℃で射出して１００×１００×３ｍｍのサイズの染料試験片を製造した。 The dye test piece was prepared by kneading and extruding 0.6 parts by weight of BK39 (manufactured by Muil Kasei Co., Ltd.) as a dye with 100 parts by weight of a thermoplastic resin composition, and then manufacturing pellets at an injection temperature of 240°C and a mold temperature. Dye specimens with a size of 100 x 100 x 3 mm were produced by injection at 60°C.
＊ゴニオクロミズム（Ｇｏｎｉｏｃｈｒｏｍｉｓｍ）現象：ＮＰ色相、顔料及び染料のそれぞれの押出ペレット及び射出試験片の外観を目視で観察し、虹色又は真珠色が発生したか否かを確認した。この中で一つでもゴニオクロミズム現象が発生した場合に“発生”と表示し、発生しない場合に“未発生”と表示する。 *Goniochromism phenomenon: The appearance of the extruded pellets and injection test pieces of each of the NP hues, pigments, and dyes was visually observed to determine whether rainbow colors or pearl colors were generated. If even one of these phenomena occurs, "occurrence" is displayed, and if it does not occur, "non-occurrence" is displayed.
前記ＮＰ色相は、着色していない樹脂固有の色であって、顔料あるいは染料を適用していないことを意味する。 The NP hue is a color unique to an uncolored resin, and means that no pigment or dye is applied.
前記表１～表３に示したように、本発明に係る熱可塑性樹脂組成物（実施例１～６）は、比較例１～１１と比較して、流動性、耐熱度、面衝撃強度及びその標準偏差がいずれも優れると共に、ゴニオクロミズムが発生せず、高黒色度が実現される効果があった。比較例１～１１はいずれも、平均面衝撃強度が２２Ｊ未満であり、標準偏差が６．５を超えて自動車の信頼性評価を満たさないため、自動車用途に適用が難しいことが確認できた。具体的には、（Ｂ－１）共重合体を含まないか、または少量含む比較例１、２及び１０は、ゴニオクロミズム現象が発生し、特に比較例１及び１０は、面衝撃強度の標準偏差が大幅に高くなった。 As shown in Tables 1 to 3 above, the thermoplastic resin compositions according to the present invention (Examples 1 to 6) had better fluidity, heat resistance, surface impact strength and All of the standard deviations were excellent, goniochromism did not occur, and high blackness was achieved. In all of Comparative Examples 1 to 11, the average surface impact strength was less than 22 J, and the standard deviation exceeded 6.5, which did not satisfy the reliability evaluation of automobiles, so it was confirmed that it was difficult to apply them to automobile applications. Specifically, in Comparative Examples 1, 2, and 10 that do not contain or contain a small amount of (B-1) copolymer, a goniochromism phenomenon occurs, and in particular, Comparative Examples 1 and 10 meet the standard of surface impact strength. The deviation has increased significantly.
また、平均粒径が１３０ｎｍであるＡＳＡ樹脂のみを含む比較例３は、シャルピー衝撃強度が劣悪となり、（Ｂ－１）共重合体と（Ｃ－１）共重合体との組み合わせを含まない比較例５～７及び９は、耐熱度が低下した。 In addition, Comparative Example 3 containing only the ASA resin with an average particle size of 130 nm had poor Charpy impact strength, and compared with the comparison not containing the combination of (B-1) copolymer and (C-1) copolymer. In Examples 5 to 7 and 9, the heat resistance decreased.
また、（Ｃ－２）ＰＭＭＡ樹脂を単独で含む比較例１１は、面衝撃強度が低く、その標準偏差は高くなった。 Furthermore, Comparative Example 11 containing (C-2) PMMA resin alone had low surface impact strength and a high standard deviation.
Claims (14)
Ａ－２）平均粒径５０～１９９ｎｍであるアクリレート系ゴム、芳香族ビニル化合物及びビニルシアン化合物を含んでなるグラフト共重合体１７～４０重量％と、
Ｂ）（メタ）アクリル酸アルキルエステル化合物、α－メチルスチレン及びビニルシアン化合物を含んでなる共重合体３０～５７重量％と、
Ｃ）ポリメタクリレート樹脂（但し、α－メチルスチレンを共重合したポリメタクリレート樹脂を除く）６～３０重量％とを含み、
ＩＳＯ ６６０３－２に準拠して、速度４．４ｍ／ｓ下で試験片の厚さ２．０ｍｍで最大荷重エネルギーを１０回測定した平均面衝撃強度が２２Ｊ以上であり、標準偏差が６．５以下であることを特徴とする、熱可塑性樹脂組成物。 A-1) 3 to 22% by weight of a graft copolymer comprising an acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide compound having an average particle size of 200 to 400 nm;
A-2) 17 to 40% by weight of a graft copolymer comprising an acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide compound having an average particle size of 50 to 199 nm;
B) 30 to 57% by weight of a copolymer comprising a (meth)acrylic acid alkyl ester compound, α- methylstyrene, and a vinyl cyanide compound;
C) 6 to 30% by weight of polymethacrylate resin (excluding polymethacrylate resin copolymerized with α-methylstyrene);
In accordance with ISO 6603-2, the average surface impact strength obtained by measuring the maximum load energy 10 times with a test piece thickness of 2.0 mm at a speed of 4.4 m/s is 22 J or more, and the standard deviation is 6.5. A thermoplastic resin composition characterized by:
製造された熱可塑性樹脂組成物は、ＩＳＯ ６６０３－２に準拠して、速度４．４ｍ／ｓ下で試験片の厚さ２．０ｍｍで最大荷重エネルギーを１０回測定した平均面衝撃強度が２２Ｊ以上であり、標準偏差が６．５以下であることを特徴とする、熱可塑性樹脂組成物の製造方法。 A-1) 3 to 22% by weight of a graft copolymer comprising an acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide compound having an average particle size of 200 to 400 nm, and A-2) an average particle size of 50 to 199 nm. 17 to 40% by weight of a graft copolymer comprising a certain acrylate rubber, an aromatic vinyl compound and a vinyl cyanide compound, and B) a (meth)acrylic acid alkyl ester compound, α- methylstyrene and a vinyl cyanide compound. After mixing 30 to 57% by weight of the copolymer consisting of C) and 6 to 30% by weight of C) polymethacrylate resin (excluding polymethacrylate resin copolymerized with α-methylstyrene), the mixture was heated at 200 to 300°C. producing a thermoplastic resin composition using an extrusion kneader at a 10-100 phi standard;
The manufactured thermoplastic resin composition has an average surface impact strength of 22 J when the maximum load energy is measured 10 times at a speed of 4.4 m/s and a test piece thickness of 2.0 mm, in accordance with ISO 6603-2. A method for producing a thermoplastic resin composition, wherein the standard deviation is 6.5 or less.
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